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Chapter 1

Introduction and review of literature

Abstract

This chapter deals with a brief introduction of the supramolecular chemistry,

various methods used for synthesis of thiacalix[n]arenes (n = 4, 6, 8) and the

functionalization of these thiacalix[n]arenes at wider rim, narrow rim and bridging

sulfur atoms. The various derivatives of the thiacalix[4]arenes prepared by carrying

out modifications at the wider rim, narrow rim and at the bridging sulphur atoms

are also reviewed. The binding behaviour of these derivatives towards different types

of cations and anions evaluated by solvent extraction method, UV-vis, fluorescence

and 1H NMR spectroscopy and their metal complexes is also presented. In the last

part of the chapter, the developments about the molecular switches, various

molecular logic gates and devices based on different molecular scaffolds are reviewed.

2


1.1 Introduction and review of literature

The understanding of the structural and functional properties of living systems is a

key challenge in chemical and biological sciences. In living systems, the non-covalent

interactions are very significant in sustaining the two and three-dimensional structure

of bio-molecules, such as proteins in which they bind specifically but transiently to

one another. Supramolecular chemistry1 which is “chemistry beyond a molecule”

provides one such platform to study the non-covalent interactions of biological

systems. This is the chemistry where molecules are able to self-organize, self-

assemble, and self-control into systems and the components are often analogues to

biological molecules. During the last few decades, there have been significant

developments in the areas of supramolecular chemistry which includes molecular

recognition, catalysis, molecular devices, self-organization, ensembles and

nanochemistry.2 Among these, molecular recognition chemistry aims at the design

and synthesis of molecular receptors which are useful to understand and mimic

nature‟s specific interactions towards various guest molecules by non-covalent

interactions. Since the origin of the concept of molecular recognition chemistry (host-

guest chemistry), a wide variety of synthetic organic receptors like crown ethers,3

cryptands,4 spherands,

5 porphyrins,

6 calixarenes,

7 thiacalixarenes,

8 and cyclodextrins

9

have been used as molecular receptors. For a molecular receptor to be an effective

host, its basic molecular scaffold should be easily synthesized and should undergo

chemical modification with designed recognition behaviour. Calix[4]arene7,10

is one

of the most actively studied molecular scaffold among the various synthetic molecular

scaffolds studied so far. Calixarenes are cyclic oligomer composed of phenolic units

linked through methylene groups possessing well defined conformational properties

and cavities of molecular dimensions which are able to encapsulate various guest

species which is a subject of interest in biomimetic chemistry. The modified

calixarene derivatives can be tuned to serve as efficient hosts towards different guest

species either by controlling their conformations or by changing the nature and

number of ligating sites. Several applications of chemically modified calix[4]arenes as

ion-selective electrodes,11

supramolecular assemblies,12

chiral shift reagents for NMR

and chiral catalysts,13

non-linear optical materials and liquid crystalline systems,14

for

antibody labeling and biological mimics,15

mimics of enzyme16

and ion channels,17

as

magnetic resonance imaging agents,18

for surface recognition of proteins,19

drug

delivery systems,20

metal oxo surface mimics,21

molecular magnets,22

photochemical

3


and electron transfer devices,23

porous surfactants,24

and nanotechnology25

have

recently been reported in the literature. Because of the above mentioned attractive

features and applications as host compounds calixarenes have been actively studied

and termed as „third generation’ 26

of the host molecules in addition to crown ethers27

and cyclodextrins.28

Kumagai et al.29

reported a second subclass of calixarene family i.e., the p-tert-

butylthiacalix[4]arene, in which all four methylene bridges of conventional

calix[4]arene are substituted by sulfide bonds. The presence of sulfur atoms makes

them an attractive host for transition metal ions. In comparison with the structural

characteristics of the conventional calix[4]arene moiety, thiacalix[4]arene is more

attractive due to the following reasons: (i) the ring size of thiacalix[4]arene is 15%

larger30

than that of calix[4]arene because of the longer covalent bond length of C-S

than C-C; (ii) ring linkages containing sulfurs may act cooperatively with phenolic

oxygen upon the binding of metal ions, and (iii) easy modification (oxidation) of the

bridging sulfur to form sulfoxide and sulfone which change the properties of the

cavity formed by the calix benzene rings, which is superior to any other calixarenes.

Thus, there is much more potential in investigating the chemistry of thiacalix[4]arenes

as artificial receptors or enzyme mimics. However, the use of thiacalix[4]arene

platform to immobilize different binding sites is still restricted because of either the

lack of derivatization methods allowing regio- and/ or stereo-selective transformations

or the unknown conformational preferences of these compounds.31

Thus, keeping in view the significance of thiacalix[4]arene in molecular

recognition chemistry, we have designed and synthesized a variety of

thiacalix[4]arene derivatives having amide, sulphonamide and (thio)urea moieties and

studied their recognition behaviour toward different cations, anions and various

neutral molecules. Before proceeding to the results of our findings, a brief review of

literature on thiacalixarenes is discussed below.

1.2 Synthesis of thiacalix[4]arene

Calixarene is a Greek word of which „calix’ means „vase‟ or „chalice‟ and

arene stands for aryl residue. Calixarenes32

are cyclic oligomers obtained from p-tert-

butylphenol and formaldehyde under basic conditions. The concentration of the base

determines which oligomer is to be formed. A variety of derivatives can be prepared

by carrying out modification at the phenolic hydroxyl group and at the para-position

4


by electrophilic substitution. Thiacalixarenes 1n (n = 1, 3, 5), on the other hand, are

cyclic oligomers obtained from p-tert-butylphenol and elemental sulfur (S8) under

basic conditions (Scheme 1.1) i.e the methylene bridges of conventional calixarene

are replaced by sulfur atoms. The first synthesis of p-tert-butylthiacalix[4]arene 11

was reported by Sone et al.33

This method involves tedious stepwise reaction of p-

tert-butylphenol and SCl2, affording p-tert-butylthiacalix[4]arene 11 in poor yield

(Scheme 1.2). However, Kumagai et al.29

reported synthesis of thiacalixarenes 1n (n =

1, 3, 5) by one step and one pot procedure which involves reaction of p-tert-

butylphenol with elemental sulfur (S8) and NaOH in tetraethylene glycol dimethyl

ether with concomitant removal of H2S (Scheme 1.3). The major product of this

reaction was thiacalix[4]arene 11 (54%) along with trace amounts of thiacalix[6]arene

13 and thiacalix[8]arene 15. Later on Kon et al.34

reported thiacalix[4]arenes 11 in

higher yield by using convergent synthetic procedure involving two steps under

alkaline conditions (Scheme 1.4). Kondo et al.35

reported the synthesis of

thiacalixarenes 1n (n = 1, 3, 5) by using acetic acid and terephthalic acid as a template

in a combination with base catalyst such as NaOH and NaH. Recently, Patel et al.36

reported an alternative approach to synthesize higher heteracalixarenes, particular

thiacalixarenes 1n (n = 1, 3, 5), by using respective homologous calixarene 2n (n = 1,

3, 5) templates (Scheme 1. 5).

OHOH HO

X

OH

XXX

OH

HCHO

OH-

S8

OH-

n Scheme 1.1: General method of synthesis of (thia)calixarenes.

SCl2

OH OHOH HO

S

OHSS S

OH OH

S

OH OH

S

OH OH

SS

SCl2 SCl2

Scheme 1.2: Four step synthesis of thiacalix[4]arene.

11

1n: X = S 2n: X = CH2

n = 1, 3, 5

5


OH

S

OHOH HOOHSS S

n

NaOH, 230oC

MeO(CH2CH2O)4MeS8+ H2S+

Scheme 1.3: Single step synthesis of thiacalixarenes.

OHOH HO

S

OHSS

S

NaOH, 200oC

Ph2OS8+

SCl2

OH OH OH

S

Scheme 1.4: Two step synthesis of thiacalix[4]arene.

OHOH HOOHn

OO OO

n

OO O O

OO OO

S

OO OOSS S

n

Route A(a) BrCH2CH2Cl, Ac2O,

M2CO3, Reflux(b) p-tert-butylphenol, Ac2O,

M2CO3, Reflux

Route BAc2O,

M2CO3, Reflux

ClO

S8, MOH in Ph2O,

230oC, 9h

or

SCl2 in CHCl3,

0oC, 2h

Reflux 2h

OHOH HOOHn

S

OHOH HOOHSS S

n

Halo-de-alkylation

LiI, Reflux,12-24 h

+

Scheme 1.5: Calixarene templated synthesis of thiacalixarenes.

Thiacalix[4]arene scaffold like conventional calix[4]arene has two rims i.e. the

narrow rim comprising of the phenolic groups, whereas the wider portion of the

1n: n = 1, 3, 5

2n: n = 1, 3,

5

2n: n = 1, 3, 5

1n: n=1, 3, 5

11

6


scaffold comprising of the para-substituent is known as the „Wider rim‟ (Fig. 1A).

Thiacalix[4]arene is capable of assuming four conformations depending upon the

orientation of the phenolic units with respect to each other37

i.e. „Cone‟ (uuuu),

„Partial cone‟, (uuud), „1,2-Alternate‟ (uudd) and „1,3-Alternate‟ (udud) as shown in

figure 1B. Thiacalix[4]arene like conventional calix[4]arene always exists in cone

conformation in the solution due to the favourable intramolecular circular hydrogen

bonding between the adjacent phenolic groups. Akdas et al.30

reported first X-ray

crystal analysis of thiacalix[4]arene which showed its cone conformation and the four

hydroxyl groups form intramolecular cyclic hydrogen bonds in solid state with C4-

symmetry. In the solution state, the 1H NMR chemical shift for the OH group of

thiacalixarenes 1n (n=1, 3, 5) in CDCl3 suggested formation of intramolecular

hydrogen bonding, the strength of which seems to be weaker than that of the

corresponding calixarenes 2n (n=1, 3, 5), respectively.38

This may be ascribed to the

enlarged skeleton of the thiacalixarene ring to separate OH groups further away from

each other. The X-ray crystal analysis showed that thiacalix[4]arene have 15% larger

bond length between aromatic residue and bridging groups which indicates that

thiacalix[4]arene cavity is larger than conventional calix[4]arene.

OHOH HO

R

S

R R R

OHSS S

Wider rim

Narrow rim

Bridging Sulfur

OHOH HO

S

OHSS S S

OR

OR

OR

SS

ORS

ROS

S

OR OR

OR

S SS

OROR

OROR

SSS

Figure 1. Various conformations of thiacalix[4]arene.

The versatility of thiacalix[4]arene 11 as host molecule is due to its chemical

modifications at wider rim, narrow rim and on the bridging sulfide group. The

(B)

(A)

Cone (uuuu) Partial Cone (uuud) 1,2-alternate (uudd) 1,3-alternate (udud)

7


chemical modifications at narrow and wider rim of thiacalix[4]arene is intrinsic to

phenols i.e. modification at the phenolic hydroxyl group and/ or the p-position.

Therefore, a variety of thiacalix[4]arene derivatives can be prepared according to well

known calix[4]arene chemistry. However presence of sulfide bonds brings steric and

electronic effects into account of thiacalix[4]arene chemistry, particularly oxidation of

sulfide bonds to sulfoxide and sulfone. Thus, reaction conditions used for the

synthesis of a particular thiacalix[4]arene derivative by carrying out modification at

the narrow rim, wider rim or bridging sulfur may considerably differ from those used

for the methylene-bridged calix[4]arene counterpart. The different types of

thiacalix[4]arene derivatives prepared by carrying out above modifications are as

follows:

1.3 Modification at wider rim of thiacalix[4]arene

1.4 Modification at narrow rim of thiacalix[4]arene

1.5 Modification at bridging sulfur atoms of thiacalix[4]arene

1.6 Binding studies of thiacalix[4]arene based receptors

1.3 Modification at wider rim of thiacalix[4]arene

Much attention has been devoted to the introduction of functional groups onto

wider rim of thiacalix[4]arene. The modification at the wider rim of thiacalix[4]arene

was carried out mainly by two processes: (i) electrophilic aromatic substitution at the

para-position of phenol residue, and (ii) direct ipso-substitution of tert-butyl groups

by electophilic agents. The Friedel-Crafts dealkylation of tert-butyl group at the wider

rim is the first reaction of this approach. The tert-butyl groups of thiacalix[4]arene

can be easily removed by a Friedel-Crafts dealkylation reaction using

AlCl3/phenol/toluene under reflux conditions to give fully de-tert-

butylthiacalix[4]arene 3.30

Higuchi et al.39

have improved the dealkylation of tert-

butyl groups of thiacalix[4]arene to large scale preparation of 3 using 10.5 equiv of

AlCl3 at 80oC with phenol. The regioselective partial dealkylation of 11 was achieved

using 7.1-7.4 equiv of AlCl3 with shorter reaction time to mono, di and tri(p-tert-

butylthiacalix[4]arene) 4-6 in 7%, 20% and 21% yield, respectively. The de-tert-

butylated thiacalix[4]arene 3 also adopts a cone conformation in solution and in solid

state like tert-butylthiacalix[4]arene 11. The X-ray structure analysis revealed that

thiacalix[4]arenes 4-6 adopt cone conformations and dimeric self-inclusion units in

such a way that phenol moieties are inserted into the cavity of each other molecules.

8


The de-tert-butylated thiacalix[4]arene 3 can be functionalized by different

electrophilic aromatic substitution reactions. The bromination and nitration of

thiacalix[4]arene by conventional methods leads to complex mixture of products due

to concomitant oxidation of sulfide linkage.40

However Lhotak et al. successfully

synthesized dibromo- derivative 7 and tetrabromo-derivative 8 of thiacalix[4]arene in

high yield by bromination of 1,3-disubstituted thiacalix[4]arene.40a

Later, Kasyan et

al. and Desroches et al. reported, independently, the synthesis of tetra-bromo

derivative 9a by direct NBS bromination of de-tert-butylated thiacalix[4]arene 3.41

Further alkylation of 9a with propyl iodide in the presence of Cs2CO3 results in tetra-

o-propylthiacalix[4]arene 9b. Desroches et al.41b

synthesized the

trimethylsilylacetylene 10 and 4-pentylphenylacetylene 11 derivatives of de-tert-

butylated thiacalix[4]arene 3 using dichlorobis(triphenylphoshane)palladium(II) as a

catalyst and shown to have potential applications in nonlinear optical applications.

The reaction of tetra-o-propylthiacalix[4]arene 9b with BuLi and N-formylpiperidine

gave p-formyl thiacalix[4]arene 12 in good yield42

which could be used as useful

starting material for various wider rim functionalizations.

S

OHOH HOOHSS

S

R1R2 R3 R4

S

OHOH OOSS

S

Pr Pr

Br Br

S

OHOH OOSS

S

Pr Pr

Br BrBr Br

S

OROR ROORSS

S

Br Br Br Br

S

OHOH HOOHSS

S

R R R R

S

OPrOPr PrOOPrSS

S

HH H HOO O O

Another significant reaction at the wider rim of de-tert-butylthiacalix[4]arene

3 is nitration. The nitration of de-tert-butylated thiacalix[4]arene 3 was achieved by

reacting with KNO3/AlCl3 to give tetranitrothiacalix[4]arene 13 in good yield without

oxidation of sulfur.43

This reaction failed in most of the organic solvents like

7 8

12

3: R1 = R2 = R3 = R4 = H 4: R1-3 = H, R4 = tBu 5: R1-2 = H, R3-4 = tBu 6: R1-3 = tBu, R4 = H

10: R =

11: R =

SiMe3

C5H11

9a: R = H 9b: R = Pr

9a-b

9


acetonitrile, tetrahydrofuran, toluene etc but surprisingly worked well in the presence

of di-, tri- or tetraglyme. The tetranitrothiacalix[4]arene 13 on reduction with SnCl2

gave tetraamino derivative 14 almost quantitatively43,44

which can be useful starting

point for wider rim derivatization. The selective nitration to dinitrothiacalix[4]arene

1545

was achieved by Hu et al. by nitration of dibenzoyl derivative of 3 followed by

debenzoylation in aqueous NaOH. Agarwal et al.46

synthesized thiacalix[4]arene

hydroxamic acids 16-18 by partial reduction of nitro-thiacalix[4]arenes with

hydrazine hydrate, Raney-Ni, and their coupling with benzoyl chloride under the

influence of microwave irradiation with excellent yields.

S

OHOH HOOHSS

S

NO2 NO2NO2 NO2

S

OHOH HOOHSS

S

NH2 NH2NH2 NH2

S

OHOH HOOHSS

S

NO2 NO2

The de-tert-butylated thiacalix[4]arene 3 was functionalized47

by Friedel-Craft

alkylations at the wider rim with 1-adamantanol and 3-carboxy-1-adamantanol in

trifluoroacetic acid with catalytic amount of LiClO4 to give

adamanthylthiacalix[4]arenes 19 and 20. The diazotization of de-tert-butylated

thiacalix[4]arene 3 with various diazonium salts results in various p-phenylazo

derivatives 21a-f.48

The reductive cleavage of 21b using Na2S2O4 and NaOH in

aqueous solution results in p-aminothiacalix[4]arene 14 which represents very useful

intermediate for further functionalization.48b

A chloromethyl group was introduced at

the wider rim of de-tert-butylated thiacalix[4]arene 3 by reacting it with excess

amount of chloromethyl methyl ester to afford 22.41a

The de-tert-butylated

thiacalix[4]arene 3 undergoes ipso-sulfonation49

by treatment with concentrated

sulfuric acid followed by salting out with sodium chloride to give 4-sulfonic acid salt

of thiacalix[4]arene 23 which is soluble in water and would expand its chemistry into

aqueous solutions.

13 14 15

10


S

SS

S

OH

OH

OH HO

R2

R2

R1 R1

S

SS

S

OH

OH

OH HO

O2N

NO2

R R

S

SS

S

O

O

OH HO

R1

R1

O2N NO2R2

S

OHOH HOOHSS S

R R R R

R =CO2H

SHO

HO

HO

HO

S

S

S

NN R

N

N R

NN R

NN R

S

OHOH HOOHSS S

ClCl Cl Cl

S

OHOH HOOHSS

S

SO3Na SO3NaSO3Na SO3Na

Kundrat et al.50

reported the formylation reactions (Gross and/or Duff

conditions) at the wider rim of the tetrapropoxythiacalix[4]arene 33 (vide infra) in the

1,3-alternate conformation. Using an excess of the formylation agent, the unexpected

regioselectivity of these reactions were noticed in which only two formyl groups were

introduced exclusively into the meta-positions of thiacalixarene skeleton 24a-c. The

formation of meta substituted aldehydes shows remarkably different reactivity of the

thiacalix[4]arene system compared with that of a classical calix[4]arene analogue. The

direct formylation of tetrapropoxythiacalix[4]arene 33 (vide infra) in the cone

conformation results in unusual products compared to formylation in 1,3-alternate

conformation.51

The Duff reaction (urotropine/TFA) leads to unprecedented

intramolecularly bridged compounds possessing two formyl groups on the opposite

para-positions or para-/meta-positions 25 or 26, respectively. The formylation results

indicate that the electronic effect of sulfur bridges and conformation of the

thiacalix[4]arene are the governing factors for the regioselectivity of electrophilic

substitution in thiacalixarene series.

19 20 22 23 21a-f

21a: R = H

21b: R = CO2H 21c: R = CH3 21d: R = OCH3 21e: R = Br 21f: R = NO2

16

NO2

N

OOH

R1 =

R2 = 17

N

OOH

R =

18

R1 =

R2 = -CH2(CH2CH2O)3CH2-

N

OOH

11


S

O O

O O

SS S

PrPr

Pr Pr R

R

S

O O

O O

SS S

PrPr

Pr Pr

R R

S

O O

O O

SS S

PrPr

Pr Pr

R R

a b c

O OO

S

OS SS

PrPrPrPr

H2C

CH=O

O=HC

O OO

S

OS S

S

PrPrPrPr

H2CO=HC CH=O

O OO

S

OS S

S

PrPrPrPr

CH=O

In comparison to Duff reaction, direct Gross formylation reaction (Cl2CH-O-

CH3/SnCl4/CH2Cl2) of tetrapropoxythiacalix[4]arene 33 (vide infra) in cone

conformation results in introduction of only one formyl group into the meta-position

of the thiacalixarene skeleton 27.52

The surprising regioselectivity indicates

dramatically different reactivity of the thiacalix[4]arene system when compared with

a calix[4]arene analogue, which yields exclusively para isomers. The introduction of

functional groups into the meta-position represents an exceptional substitution pattern

in thiacalixarene chemistry, which imparts an interesting conformational behaviour to

these compounds.

1.4 Modification at narrow rim of thiacalix[4]arene

The narrow rim (phenolic hydroxyl group) of thiacalix[4]arene undergoes two

types of reactions i.e. alkylation and esterification. The narrow rim functionalization

of calix[4]arene is well established in literature but alkylations with simple alkyl

halides under same conditions did not give the same conformational outcomes in

thiacalixarene chemistry. The presence of four sulfur atoms in thiacalix[4]arene

imparts many novel features that reflect significantly different behaviour and

conformational preferences of thiacalix[4]arene upon functionalization.

The alkylation of p-tert-butylthiacalix[4]arene 11 and de-tert-

butylthiacalix[4]arene 3 with alkyl halides in the presence of base generally gives

24a-c: R = -CH=O

25 26 27

12


tetraalkylated products in good yield.53

Lhotak et al. prepared a series of tetra 28-35

and partially methylated 36-38 thiacalix[4]arene derivatives and studied their

conformational preferences using NMR spectroscopy and X-ray crystallography. The

conformer distribution of these alkylated products is different from that of

calix[4]arene and found that 1,3-alternate conformers are obtained in high yields

while the cone conformation forms only in low yields.

S

S

S

S

O

O

O

O

XX

XX

R1

R4

R3

R2

The etherification of thiacalix[4]arene with ethylbromoacetate in the presence

of alkali carbonates (M2CO3, M = Li+, Na

+, K

+ and Cs

+) as base in acetone yields

different acetate derivatives of thiacalix[4]arene i.e. cone 39a-b, partial cone 39c-d

and 1,3-alternate 39e-f.54

The conformational distribution of these isomers depends

upon the type of metal carbonate which exhibits pronounced metal template effect and

is the governing factor for these conformations. Lhotak et al.55

synthesized lactone

derivatives 40a-b and 41a-b from diacetate of thiacalix[4]arene by an unprecedented

intramolecular cyclization. Compounds 40a and 40b showed an interesting π-π and

hydrogen bonding interactions as determined by the X-ray crystallography. These

interactions make compounds 40a and 40b inherently chiral compounds which were

demonstrated through their separation on a chiral HPLC column. The direct

aminolysis of tetraacetate of cone and 1,3-alternate conformations with aliphatic

diamines results in proximally bridged thiacalix[4]arenes 42a-c and 43a-b,

respectively.56

Further, Stastny et al.57

reported doubly bridged thiacalix[4]arenes

44a-c in the 1,3-alternate conformation by direct aminolysis reaction of

thiacalix[4]arene tetraacetates with α,ω-diamines. Both sites of 1,3-alternate

conformer intramolecularly bridged to form the cagelike structures in high yields. The

structural analysis of the novel cagelike molecules revealed a highly preorganized

array of -C(O)-NH- bonds pointing to the interior of the cavity. Liu et al.58

also

synthesized bicyclic amides 45a-b and single crystal X-ray diffraction analysis

28-38

28 29 30 31 32 33 34 35 36 37 38

X But H Bu

t H Bu

t H Bu

t H H H H

R1 Me Me Et Et Pr Pr Bu

t But H H H


t But H Me Me


t But H H Me


t But Me Me Me

Table 1. Base catalyzed alkylated products of thiacalix[4]arene.

13


showed that these bicyclic amides of thiacalixarene exist mainly in 1,3-alternate

conformation.

OO O

R

S

R R R

OSS

S

EtO

O

EtO

O

OEt

O

OEt

O

Cone

SO

O

RRR

R

O

SS

Partial cone

O

S

EtO

O

EtO

O

EtOO

EtO

O

S

OO

O

R

R

R

R

O

SSS

1, 3-alternate

OEt

O

OEt

OEtO

O

EtO

O

OO O

R

S

R R R

OSS

S

O O

OS

S

O O

R

RR

R

O

SS

O

O

OO O

S

OSS S

HN

O

HN

O

HN

O

HN

O

n n

S

OO

OO

SSS

HNO

NHO

NH

O

HN

O

n

n

S

O O

O O

SS S

O

OO

O

HNNH

HNNHR R

RR

S

OO

OO

SSS

O

O O

O

NH HN

NH

R

HN

R

Morohashi et al.59

selectively synthesized conformational isomers of 46a in

cone and 1,3-alternate conformations directly from tert-butylthiacalix[4]arene 11

using NaH and Cs2CO3 as base, respectively. However, three to four-steps were

required for benzylation of p-tert-butylthiacalix[4]arene 11 to get partial cone and 1,2-

alternate isomers, respectively. Similarly, Yamato et al.60

synthesized tetra-

39a: R = But

39b: R = H

39a-b

39c: R = But

39d: R = H

39c-d

39e: R = But

39f: R = H

39e-f

40a: R = But

40b: R = H

40a-b

41a: R = But

41b: R = H

41a-b

42a: n = 0 42b: n = 1 42c: n = 2

42a-c

43a: n = 0

43b: n = 1

43a-b 44a: R = H 44b: R = Bu

t

44c: R = Ph

44a-c

45a: R = CH2CH2

45b: R = CH2CH2CH2

45a-b

14


kis(pyridylmethoxy)-thiacalix[4]arene 46b and 46c of cone and 1,2-alternate

conformations by reaction of 11 with 2- and 4-(chloromethyl)pyridine in the presence

of Cs2CO3 as base.

The intramolecularly bridged (1+1) or intermolecularly bridged (2+2) products

47a-d and 48a-d of calix[4]arene or thiacalix[4]arene have been reported by Xiong et

al,61

using bis(tosyloxyethoxy)benzenes as bifunctional reagents. It was found that the

bridging pattern strongly depended on the structure of bis(tosyloxyethoxy)benzene

and the kind of calixarene moiety. For the ortho-isomer of

bis(tosyloxyethoxy)benzene, intramolecularly bridged calix[4]arene and

thiacalix[4]arene were the main products. For the para-isomer, the bridging reaction

was in a (2+2) fashion.

S

S

S

S

RO

OR

OR

RO

ButBut

ButBut

OHOH O

X

OXX

X

R

OH

OH

O

X

O

X

X

XHO

HO

O

X

O

X

X

X

R

R

OHOH RO

S

OR

SSS

OHOH O

S

O

SSS

EtO2C CO2Et

R R

46a-c

46a: R =

NH2C

NH2C

H2C

46b: R =

46c: R =

49a: R = Me 49b: R = Bu 49c: R = Oct 49d: R = PhOCH2CH2 49e: R = Cl(OCH2CH2)2 49f: R = Me(OCH2CH2)2 49g: R = Br(CH2)6

49h: R = Cl(CH2)6

49a-h

47a: X = CH2, R =

47b: X = CH2, R =

47c: X = S, R =

47d: X = S, R =

O O

OO

O O

OO

47a-d

48a: X = CH2, R =

48b: X = CH2, R =

48c: X = S, R =

48d: X = S, R =

O O

OO

O O

OO

48a-d

50a: R = (R)-Me

50b: R = (S)-Ph

50a-b

15


Bitter et al.62

carried out the regioselective distal alkylation of

thiacalix[4]arene with alcohols using Mitsunobu protocol. By using this protocol only

regioselective stable cone conformation was formed with distally substituted

derivatives 49a-h and the reaction generally stopped at the disubstitution stage and tri-

or tetraethers could not be isolated. This protocol has been proven to be one of the

effective tools in functionalization of chiral/achiral thiacalix[4]arenes 50a-b in stable

cone conformation with distally substituted derivatives. Csokai et al. reported

intermolecular couplings versus intramolecular ring closures in the reaction of p-tert-

butylthiacalix[4]arene 11 and diethylene glycols affording dimers 51a-b and/or the

inherently chiral 1,2-thiacalix[4]crown-3 derivatives 52a-b and monocrowns 53a-e

using the Mitsunobu protocol.63

Furthermore, Mitsunobu protocol was extended for

cyclization of p-tert-butylthiacalix[4]arene 11 with glycols to oligoethylene glycol

analogues composed of O, S, and N atoms in the chain to produce various

monocrowns such as 54-57.

O

O

HO

S

HO

S

S

SO

O

OH

S

OH

S

S

SR

R

OHO O

S

OSS

S

R RHO

OHOH O

S

OSS

S

R

OHOH O

S

OSS

S

NS S

S

OO

OO

SSS

NS S

Oct Oct

S

OO

OO

SSS

NX X

PrO OPr

R

Thiacalix[4]arene 11 also undergoes regioselective O,O’-difunctionalization at

the neighbouring phenol hydroxyl groups. The treatment of thiacalix[4]arene with

54 R = -Ph-N=N-Ph-NO2 56: X = O 57: X = S

55

52a: R = S

52b: R = NPh

52a-b

53a: R = OCH2CH2O 53b: R = (OCH2CH2O)2 53c: R = (OCH2CH2O)2NPh 53d: R = (OCH2CH2O)2NBn 53e: R = (OCH2CH2O)2-1,2-C6H4

53a-e 51a: R = S

51b: R = NPh

51a-b

16


1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane provides the proximally-bridged

compound which on reaction with alkyl halide in the presence of base gave 1,2-

alternate O”,O”’-dialkylated products 58a-d.64

The proximally-bridged compound is

very useful synthetic intermediate for 1,2-disubstitution of thiacalix[4]arene,65

for

example, both syn and anti-1,2-bis(O-2-aminoethyl)ethers of thiacalix[4]arene 59 and

60 were prepared stereoselectively by reaction of 58a with chloroacetonitrile followed

by reduction. Narumi et al.66

synthesized 1,2-bridged monocrowns 61a-d by reaction

of disiloxane-capped 58a with different oligoethylene glycol ditosylate using Cs2CO3

as the base which were desilylated using tetrabutylammonium fluoride. Serizawa et

al.67

reported a dialkylation of the proximal OH groups of thiacalix[4]arene by

protecting two proximal OH groups with tiflate moieties to give 62 by intramolecular

rearrangement of 1,3-bistriflate ester to its 1,2-counterpart, followed by anti-selective

dialkylation of the remaining OH groups with alkyl halides or using Mitsunobu

conditions and subsequent removal of the triflate moieties.

OS

S

OO

O

SS

RR

Si Si

O

OHO HO

S

O

SS S

NH2 NH2

SO

O

OH

SS

OH

S

NH2

NH2

OHO HO

S

OSS

S

On

OTfOH TfO

S

OH

SSS

OHOH O

S

O

SSS

O O

S

S

S

S

RO

OR

OR

RO

XX

XX

59 60

63 62

58a: R = H 58b: R = Me 58c: R = CH2CO2Et 58d: R = CH2Ph

58a-d

64a-d

64a: X = But, R =

64b: X = H, R =

64c: X = But, R =

64d: X = H, R =

N

N

N

N

61a: n = 0 61b: n = 1 61c: n = 2 61d: n = 3

61a-d

17


The acylation of thiacalix[4]arene has been little explored compared to

etherification. Hu et al.45

reported a dibenzoylated derivative 63 of de-tert-butylated

thiacalix[4]arene 3 by reacting with benzoyl chloride. The reaction of

thiacalix[4]arene and de-tert-butylated thiacalix[4]arene 3 with isonicotinoyl or

nicotinoyl chloride afforded tetraacylated derivatives 64a-d in all four

conformations.68

Recently Simanova et al.69

reported the acylation of

thiacalix[4]arenes with acetyl chloride or acetic anhydride which gave the

corresponding narrow rim tetraacetoxy derivatives 65a-f which are conformationally

mobile in solution and represent a thermodynamical equilibrium of different

conformers at room temperature. The conformational preferences of acetylated

thiacalix[4]arenes mainly depend on the wider rim substitution. The tetraacetoxy

derivatives of p-tert-butylthiacalix[4]arene prefers 1,3-alternate 65b and 1,2-alternate

conformations 65f (43 and 38%, respectively), while the wider rim unsubstituted

derivative adopts preferably the partial cone conformation 65c (70%).

OS

S

O O

R R

O

S SS

OO

OO

SS

S

H3C

CH3 H3C

CH3R R

R R

RR

O O

O O

CH3

O

CH3

O

H3C

O

H3C

O

SO

O

RR R

R

O

SS

O

S

CH3 CH3

H3C

CH3

O O O

O

Tyuftin et al.70

synthesized ω-bromoalkoxy derivatives 66a-e (n = 2-6),

thioacetates 67a-d (n = 2-5). The hydrazinolysis of the thioacetates 67a-d (n = 2-5)

results in thiol derivatives 68a-d (n = 2-5) which is the most efficient method for the

synthesis of thiols. Stoikov et al.71

developed a regioselective synthesis of new

thiacalix[4]arenes derivatives 69a-c, 70 and 71 functionalised with amide groups at

the narrow rim in cone, partial cone and 1,2-alternate conformations by treating the

thiacalix[4]arene with N-(p-nitrophenyl)-α-bromoacetamide in the presence of M2CO3

(M = Na, K and Cs). It was observed that the formation of two different disubstituted

compounds i.e. distal disubstituted thiacalixarene in cone conformation and proximal

disubstituted thiacalixarene in 1,2-alternate conformation, is possible depending on

65a-b

65a: R = H

65b: R = But

65c-d

65c: R = H

65d: R = But

65e-f

65e: R = H

65f: R = But

18


the nature of the base. Polivkova et al.72

reported unexpected behaviour of

monospirothiacalix[4]arene 72a under acidic conditions. The treatment of the

monospirothiacalix[4]arene derivative 72a with various acidic agents (HCl or HBr)

results in rearrangement of the thiacalixarene skeleton leading to the formation of a

phenoxanthiin derivative 72b.

S

OROR

OROR

SSS

OR3OR2 R4O

S

OR1

SSS

R4OS

S

OR2 OR3

OR1

S S

SOR4

OR1

OR3

SS

OR2

S

S

S

S

S

HO

OHO

ButBut

ButBut

O

S

S

S

S

HO

OH

OH

O

ButBut

But

But

Antipin et al.73

reported first phosphorylated thiacalix[4]arene 73 by reaction

of thiacalix[4]arene 11 with an excess of PCl3. The bis-chlorophosphate

thiacalix[4]arene 73 adopts the 1,2-alternate conformation. However, reaction of 11

with 2 equiv of PCl3 in the presence of Et3N and subsequent condensation with

72a

66a-e: R = (CH2)nBr 67a-d: R = (CH2)nSC(O)CH2

68a-d: R = (CH2)nSH

n = 2, 3, 4, 5, 6 a, b, c, d, e

72b

69 a-c

R1 = NO2H2COCHN , R2 = R3 = R3 = H

R1 = R2 = NO2H2COCHN , R3 = R3 = H

R1 = R2 = R3 = NO2H2COCHN , R3 = H

69 a:

69 b:

69 c:

70

R1 = R2 = NO2H2COCHN

R3 = R3 = H71

R1=R2=R4= NO2H2COCHN

R3 = H

19


diethylamine led to isolation of the diester amide 74 without oxidation.74

Kasyan et

al.75

synthesized a thiacalix[4]arene substituted by four carbamoylmethylphosphine

oxide groups at the wide rim forms hydrogen-bonded, dimeric capsules 75a-c with S8

symmetry in the crystalline state and in apolar solvents. The dimeric capsule was held

together by intermolecular –N–H…O=P– hydrogen bonds. The structure was

confirmed by single-crystal X-ray crystallography.

OS

S

O O

O

S S

P

OCl

PCl O

OS

S

O O

O

S S

P

NEt2

P

Et2N

OHOH HO

S

OHSS S

HN

P

Ph Ph

O

O

NH

P

PhPh

O

ONH

P

PhPh

O

OHN

P

Ph Ph

O

O

S

S

S

S

H2N

NH2

NH2

H2N

ButBut

ButBut

S

S

S

S

HS

SH

SH

HS

ButBut

ButBut

Thiacalix[4]arene can undergoes complete replacement of phenolic OH groups

by NH2 and SH groups as in the calix[4]arene chemistry. Katagiri et al.76

used

chelation–assisted SNAr methodology for the synthesis of

tetraaminothiacalix[4]arenes 76 which is a useful molecular platform for synthesis of

new functional materials. On the other hand, Rao et al.77

successfully synthesized p-

tert-butyltetramercaptothiacalix[4]arene 77 by replacing OH groups by SH groups.

This was achieved by a series of reactions i.e. acylation of 1 with N,N-

dimethylthiocarbamoyl chloride producing O-thiocarbamoyl derivative which was

thermally converted into S-carbamoyl derivative and then deprotection with hydrazine

hydrate gave 77 in good yield. The X-ray crystallography revealed that mercapto

73

74

77 76

75a: X= S 75b: X= SO

75c: X= SO2

75a-c

20


derivative 77 adopts the 1,3-alternate conformation in the solid state in contrast to

thiacalix[4]arene 11. Katsyuba et al.78

demonstrated the role of different substituents

at the narrow and wider rims and the type of interphenolic junctions in conformational

behaviour and binding abilities of the thiacalix[4]arene molecules. Quantum-chemical

computations in combination with IR and NMR spectroscopy prove that, in contrast to

closely related calixarenes, the 1,3-alternate becomes a dominant conformer of p-tert-

butyl-mercaptothiacalix[4]arene 77 not only in crystal, but also in solutions and in

vacuum. The replacement of OH groups by SH groups in mercaptothiacalixarene 77

results in essential loss of cooperativity of the intramolecular H-bonding. The four SH

groups are intramolecularly H bonded to the bridging S atoms solely as a result, the

SH---S bonding almost equally stabilises all the conformations, and the energy gap

between the cone and other conformations of 77 is much smaller than in the case of

calixarenes. Further the replacement of OH group by SH group transform cone

conformation to pinched-cone conformer. On the other hand, the introduction of four

tert-butyl groups into wider rim of the molecule 77 increases destabilization of the

cone, which, in turn, results in domination of the 1,3- alternate conformer where the

repulsion of the tert-butyl groups is minimal.

1.5 Modification at bridging sulfur atoms of thiacalix[4]arene

One of the unique features of thiacalix[4]arene compared to classical

calix[4]arene is the presence of sulfide group which can undergo oxidation to sulfinyl

and sulfonyl function. Treatment of thiacalix[4]arene with an oxidant such as

hydrogen peroxide/trifluoroacetic acid or sodium perborate in an organic acid solvent

converted all four sulphide bonds to sulfone derivatives 78a-b and sulfoxide

derivatives 79a-b.79

Structural analysis made by Mislin et al.79a

showed that sulfonyl

derivatives 78a-b prefer 1,3-alternate conformation which is held together by 3D

network of inter- and intra-molecular hydrogen bonds between phenolic groups and

sulfonyl oxygens. The sufoxide derivatives 79a-b, having free rotations of the phenol

subunits, adopts four different stereoisomeric forms (rccc, rcct, rctt and rtct) due to

disposition of the tetrahedral sufoxide moiety. While attempting for ipso-nitrations of

tetraacetate of 11, Lhotak et al.80

noticed no nitrated product but instead identified

sulfoxide derivatives 80a-d. The regio- and stereocontrolled oxidation of sulphide to

sulfoxide function was also reported using NaNO3-CF3CO2H reagent.80

21


X

OHOH

OHOH

XXX

R

R

R

R

S

S

S

S

HO

OH

OH

HO

ButBut

ButBut

S

SS

S

OROR RO

Y

S

Y Y Y

ORSS

SO

OOO

S

SS

S S

SS

S S

SS

S S

SS

S

O O

OO

O O

O

O

O O

OO

O

OO

O

1.6 Binding studies of thiacalix[4]arene based receptors

The presence of sulfur atoms (which possess lone pairs of electrons and vacant

3d orbitals) in thiacalix[4]arene results in many novel features, especially in the field

of metal ion complexation. Compared to conventional calix[4]arene which itself has

poor binding ability towards transition metal ions, thiacalix[4]arene has varying

metal-recognition ability and this ability is improved by introducing different ligating

functional groups. Thiacalix[4]arene 11 was found to extract a wide range of transition

metal ions from aqueous solutions.81

The complexation ability of sulfones 78a-b and

sulfoxides 79a-b derivatives of thiacalix[4]arene 11 was also systematically studied

and found to have intrinsic participation in metal ion complexations.79b,c

These results

can be categorized as follows: (1) 11 prefers to complex soft-to-intermediate metal

ions (e.g. Ag+, Zn

2+, Cd

2+, Cu

2+, Hg

2+); (2) sulfones 78a-b extracts hard metal ions

(e.g. alkaline earth metals, lanthanoids), and (3) sulfoxides 79a-b represents a

somewhat intermediate situation and extracts both the above mentioned groups of

metals. These results enable us to speculate about the binding modes of

thiacalix[4]arenes. The proposed binding modes of 11, 78a-b and 79a-b are depicted

schematically in figure 2 which shows the binding of 11 towards soft metal ions, 78a-

b toward hard metal ions and 79a-b toward soft and hard metal ions. The sulfoxide

79a-b can switch between an interaction involving the sulfoxide lone pair or its

oxygen, depending on the coordinating metal. One more interesting feature of

11

79a (rccc)

79a (rcct) 79a (rctt) 79a (rtct)

78a: R = But, X= SO2

78b: R = Octt X= SO2

79a: R = But, X= SO

79b: R = Octt X= SO

78a-b 79a-b

80a: Y = But, R = Me

80b: Y = H, R = Me

80c: Y = H, R = Pr

80d: Y = But R = CH2CO2Et

80a-d

22


thiacalix[4]arene 11 is inclusion of organic molecules within their cavities formed by

aromatic rings or in the crystal lattice. The inclusion behaviour was studied using

NMR and X-ray structural analysis.30, 38b, 82

O- -O

R

S

R

SS

M

O- -O

R

S

R

SS

M

O

OO- -O

R

S

R

SS

M

O

O- -O

R

S

R

SS

M

O

Figure 2. Proposed binding modes of thiacalix[4]arene 11, its sulfone 78 and sulfoxide derivative 79.

Thus, the presence of sulfur atoms in thiacalix[4]arene moiety which is a soft

donor leads to soft metal ion recognition and the incorporation of oxygens in

functionalized thiacalix[4]arenes drifts the binding affinity from soft metal ions to

hard metal ions. Therefore functionalization of thiacalix[4]arene with suitable ligating

sites like N and S/ hydrogen bond donors in a specific design would lead to suitable

receptors selective for sensing of soft metal ions and anions. Thiacalix[4]arene

scaffolds, having vast possibilities of functionalization at the wider, narrow rim and at

the sulfide groups, have been decorated in different ways to form different types of

host molecules like thiacalix[4]podands, thiacalix[4]crowns and bisthiacalix[4]arenes.

Further, the modification at the sulfide groups make its chemistry interesting in

aqueous medium as well which is not seen in the case of conventional calix[4]arene

chemistry.

In general, many efforts have been devoted for development of

thiacalix[4]arene based derivatives for molecular recognition of various analytes

(cations, anions and neutral molecules). The recent developments of recognition of

cations, anions and neutral molecules based on thiacalix[4]arene derivatives have

been discussed as follows:

1.6.1 (Thia)calix[4]arene based receptors for cations

Thiacalix[4]arene 11 itself was found to have strong binding affinity towards

transition metal ions. Ali et al. applied thiacalix[4]arene 11 to a component of thin

films for electrolyte-insulator-semiconductor (EIS), ion-sensitive field effect transistor

Soft

Hard

Soft

Hard

11

79

78

79

23


(ISFET), and gold microelectrodes, which allowed detection of Cu2+

at a level of as

low as 10-7

M.83

This affinity of metal ion recognition could be enhanced by

introducing different ligating functional groups. Various thiacalix[4]arene based

ligands have been prepared by introducing different functional groups such as ether,84

ester,54

ketones,85

amide,86

phosphine oxide,87

etc. Generally, the coordination ability

of thiacalix[4]arene derivatives was investigated by solvent extraction of metal ions

from aqueous phase to organic phase or by 1H NMR, UV and fluorescence

spectroscopy. Lamartine et al.88

reported compound 81 containing amide groups

which show significant complexation ability toward K+, Rb

+ and Ag

+ cations. A series

of 1,3-alt-thiacalix[4]arenes 82a-c containing different isomeric aminopyridyl

pendant arms have been synthesized by Li et al.89

The crystal structure of meta-

aminopyridyl derivative demonstrate intramolecular hydrogen bondings between the

sp2 nitrogen donors in the meta position of the aminopyridyl groups and the facing

amide N–H of the adjacent aminopyridyl groups, and self-assembles via C–H O

weak hydrogen bondings and C–H π interaction to generate a double stranded

rectilineal networks. By contrast, the para-aminopyridyl derivative forms N–H N

strong hydrogen bonds between the individual molecules. Further it was found that

meta-aminopyridyl derivative showed the best extraction capacity toward Ag+ ion.

OO O

S

OSS S

Et2N

O

NEt2

ONEt2

O

Et2N

O

S

O O

O O

SS S

HN

R

NHR

OO

NH

R

HN

R

OO

S

O O

O OSS S

N N

R R

A series of thiacalix[4]podands 83a-c90

and bisthiacalix[4]arenes 84a-b90

and

85a-d91

with imine units have been reported by Bhalla et al, and have shown that

these thiacalix[4]arene derivatives quantitatively and selectively extracted Ag+ ion

from aqueous phase into organic ones. These extraction results were much better than

those in the case of conventional biscalix[4]arene units.92

81 83a-c

N

S

HO

83a: R =

83b: R =

83c: R =

82a-c

N

N

N82a: R =

82b: R =

82c: R =

24


O

ON

NO

O N

N

R

R

S

O

OS

S

S

S

O

OS

S

S

SHO

HO

O

O

S

S

S

N

N

SOH

OH

O

O

S

S

S

N

N

R

R

Stoikov et al.93

synthesized morpholidine and pyrrolidine-appended

thiacalix[4]arene derivatives of cone 86-87, partial cone 94-95, and 1,3-alternate 102-

103 conformations (Table 2). The picrate extraction and dynamic light scattering

(DLS) methods were used to evaluate recognition properties of 86-87, 94-95, and

102-103 for monocharged cations (Li+, Na

+, K

+, Cs

+ and Ag

+). It was shown that all

derivatives of thicalix[4]arene form nanoscale particles with silver cations. The

pyrrolidine derivative in cone conformation showed both self-association and

aggregation behaviour with lithium cations. The degree of extraction that formed

nanoscale aggregates in the organic phase was more than 67% which offer

opportunities for development of new materials with extended antibacterial properties,

„smart‟ materials in nanolithography and nanochip technologies (multiple analyte

detection). Further, Stoikov et al.94

evaluated these receptors for cation recognition of

p-(Al3+

, Pb2+

) and d-(Fe3+

, Co3+

, Ni2+

, Cu2+

, Cd2+

, Hg2+

) elements by the picrate

extraction method, dynamic light scattering (DLS), and atomic force microscopy

(AFM). It was observed that thiacalixarenes tetrasubstituted by the pyrrolidide group

were effective extractants compared to morpholide groups and were able to form

dimers of about 1.0 nm with metal cations and nanoscale particles of 238 and 212 nm

with Ni2+

and Pb2+

cations, respectively. The size of the particles consisting of metal

cations and tetrasubstituted thiacalix[4]arenes depends on the configuration of

macrocycles and the nature of the substrate and their binding centers.

84a-b

N84a: R =

84b: R =

85a-d

N

S

85a: R =

85b: R =

85c: R =

85d: R =

25


S

OO OOSS

S

R RRR OO OO

SO

O

O

SS

O

S

RO

R O

RO

RO

S

OO

OO

SSS

R R

RR

OO

OO

Further, Yushkova et al.95

synthesized thiacalix[4]arenes based receptors

functionalized with secondary amide and hydrazide groups at the narrow rim in cone

88-93, partial cone 96-101, and 1,3-alternate 104-109 conformations and studied the

self-assembly and recognition behaviour of metal ions of s-(Li+, Na

+, K

+, Cs

+), p-

(Al3+

, Pb2+

) and d-(Fe3+

, Co3+

, Ni2+

, Cu2+

, Ag+, Cd

2+, Hg

2+) block elements by picrate

extraction method and dynamic light scattering (DLS). The DLS method was used for

determination of the hydrodynamic diameter, polydispersity index, and molecular

weight of nanoscale aggregate systems consisting of thiacalix[4]arene molecules and

metal nitrates. It was seen that all these p-tert-butylthiacalix[4]arenes derivatives bind

to alkaline metal cations with low efficiency.96

Silver ions were the only exception

because of their complexation at “soft” sulfur atoms. A similar tendency was observed

for p-tert-butylthiacalix[4]arenes 93, 101, 109 functionalized with hydrazide groups.

This is due to insufficient electron donating ability of the substituents at carbamoyl

groups as well as to the strong hydrogen bonding between the protons of NH groups

and amide carbonyls which compete with the coordination of the cations with

phenoxyl oxygen atoms and amide carbonyls. The stereoisomers 93, 101, 109 showed

86-93

Cone

94-101

Partial Cone

102-109

1,3-alternate

Cone Partial cone 1,3-alternate R

86 94 102 NO

87 95 103

N

88 96 104

NH-

89 97 105

CH2NH-

90 98 106 CH3(CH2)7-NH-

91 99 107 CH3(CH2)11-NH- 92 100 108 CH3(CH2)13-NH-

93 101 109 NH2NH-

Table 2. Thiacalix[4]arenes based amide receptors 86-109.

26


certain affinity not only toward silver cations but toward some cations of p- and d-

elements. The increase in extraction ability of the compounds 93, 101, 109 toward

“soft” cations can be explained by the introduction of an additional center for metal

coordination i.e. lone electron pair of terminal nitrogen atoms of hydrazide groups. 97

The DLS method showed that aggregates of stereoisomers 93, 101, 109 with nitrates

of p- and d-metals are inclined to form nanosized aggregates but not to self-associate.

All the investigated compounds form nanoscale aggregates with silver(I), copper(II),

and iron(III) cations under experimental conditions but do not self associate. The

binding properties of hydrazine derivative of thiacalix[4]arene of cone 93 and 1,3-

alternate 109 conformations were evaluated by means of liquid–liquid extraction for a

large variety of metal ions.98

The cone conformer of thiacalix[4]arene shows higher

selectivity in a series of d-metal ions compared with its “classical” analogue. The

extraction selectivity for Cu2+

and Hg2+

over another transition metals becomes very

excellent when going from cone to 1,3-alternate conformation of thiacalix[4]arene.

Solovieva et al.99

reported the narrow rim thiacalix[4]arenes 110-127 (Table 3)

of cone and 1,3-alternate conformations containing four carbonyl groups. The

extraction studies showed that the removal of the tert-butyl groups decreases the

extraction ability of the macrocycles and the selectivity can either increase or decrease

depending on the nature of the stereoisomer. The compound 117 in the cone

conformation is an efficient and selective extractant for the Li+ cation, and compounds

124 and 125 in the 1,3-alternate conformation are selective extractant of the Cs+ ions.

An increase in the lipophilicity of compounds 118 and 127 in the absence of tert-butyl

groups at the wider rim exerts no effect on the extraction of the alkaline metal cations.

It was observed that the main factor of lower extraction ability of the unsubstituted

thiacalixarenes at the wider rim was the absence of the preorganization effect of

macrocyclic platform.

S

OO O

R1R1R1 R1

OSS

S

R2R2R2R2

OO OO

S

OO

OO

SSS

R1

R1

R1

R1

R2 R2

R2R2

OO

OO

Cone

110-118

1,3-alternate

119-127

27


The (thia)calix[4]arene derivatives 128a-g100

bearing two to four

thiophosphate substituents were found to be quantitatively selective for Ag+ (%

Extraction = 99). Extraction and complexation levels increase with the number of

thiophosphates groups. The S atoms of thiacalix[4]arene moiety and thiophosphate

may serve as a two-electron donor to a Ag+ ions. The results show that thiacalixarenes

in general are better extractants than calixarenes suggesting the contribution of the

bridging sulfur to the coordination.

S

OHOH OOSS S

O O

CH

NR

CH

NR

S

OHOH OOSS S

O O

HC

N

CH

NR

Yang et al.101

reported various thiacalix[4]arenes based podands 129a-d

containing aromatic hydrazide groups like salicylic hydrazide, nicotinic hydrazide,

isonicotinic hydrazide using „„1+2‟‟ intermolecular condensation and cyclic

derivatives 130a-d containing o-phenylendiamine, oxalyl dihydrazide, malonic

dihydrazide and adipic dihydrazide by „„1+1‟‟ intermolecular condensation. Further,

they synthesized hydrazone-bridged bis(thia)calix[4]arene 131 by condensation of

thiacalix[4]arene-dialdehyde with 1,3- bis(hydrazinocarbonyl-methoxy)-calix[4]arene.

Cone 110 111 112 113 114 115 116 117 118

1,3-alternate

119 120 121 122 123 124 125 126 127

R1 But H Bu

t Bu

t Bu

t H H H H

R2 H H OEt Ph NEt2 OEt Ph NEt2 NBu2

Table 3. Thiacalix[4]arenes based receptors 110-127.

129a-d

129a: R =

129b: R =

129c: R =

129d: R =

CONH

OH

N

CONH

N CONH

130a-d

130a: R =

130b: R =

130c: R =

130d: R =

NH

NH

O

O

NH

NH

O

O

NH

NH

O

O

(H2C)4

OR3OR2 R4O

X

OR1

XX X

128a-g

128a: X = S; R1 = R3 = H; R2 = R4 = Y 128b: X = S; R1 = H; R2 = R3 = R4 = Y 128c: X = S; R1 = R2 = R3 = R4 = Y 128d: X = CH2; R1 = R3 = H; R2 = R4 = Y 128e: X = CH2; R1 = H; R2 = R3 = R4 = Y 128f: X = CH2; R1 = R3 = CH2CO2Et; R2 = R4 = Y

128g: X = CH2; R1 = CH2CO2Et; R2 = R3 = R4 = Y

Y = P

OOEt

OEt

28


The non-competitive and competitive extracting experiments showed that these novel

hosts were good receptors for both metal cations and α-amino acids. Compounds

129a-d and 130a-d showed similar binding properties with high extraction percentage

but low extracting selectivities. Bis(thia)calix[4]arene 131 exhibited not only high

extracting abilities but also good extracting selectivities.

Lamare102

and Grun103

et al. reported thiacalix[4]crowns of 1,3-alternate

conformations; thiacalix[4]bis(crown-5) 132a and –bis(crown-6) 132b and have

shown to have remarkable selectivity towards K+ and Cs

+ ions. The biscrown 132c

showed high selectivity for Cs+ over K

+. van Leeuwen et al.

104 studied in detail the

reaction of thiacalix[4]arene with oligoethylene glycol ditosylate catalysed by alkali-

metal carbonate to give thiacalix[4]crowns of cone, 1,3-alternate and 1,2-alternate

confomations and found that thiacalix[4]crowns 133a-c, 134a-b and 135a-b showed

high extraction ability towards Ag+ ion over the alkali metal ions. The modified

thiacalix[4]crowns 136a-b105

show high selectivity for Ra2+

even in the large excess

of over other common alkali and alkaline-earth metal cations. The selective extraction

of Ra2+

has attracted much interest because the ion is found in trace amount of

naturally occurring radioactive materials in aqueous waste stream of non-nuclear

industries.

S

OO

OOS SS

OO

OO

O O

OO

n

n

OO HO

S

OHSS

S

OO

O

n

S

OO

OO

SSS

OO

O

O

OO

n

n

OS

S

O O

O

SS

OOO

O

OO

n

n

131

132a: n=0 132b: n=1 132c: n=2

132a-c

133a: n=0 133b: n=1 133c: n=2

133a-c

134a: n=1 134b: n=2

134a-b

135a: n=0 135b: n=1

135a-b

SOH

OH

O

O

S

S

S

O

O

HC

HC

HO

HO

O

ONH

HNN

O

O

N

29


OO O

S

OSS

S

OO

OHO2CH2C CH2CO2Hn

S

O

O

O

S

S

S

R

R

O

O

O

O O

O O

S

O

O

S

S

S

R

R

O

O

O

S

O

S

S

SO

O

O

S

O

S

S

S

The thiacalix[4]arene dimer 137106

of 1,3-alternate conformation shows high

affinity toward Cs+ and K

+ ions. Encapsulation of Cs

+ by the internal cavity of the

dimer strongly suggests that the size match factor drives the process. On the other

hand, the K+ is encapsulated by the thiacalix[4]arene units by supramolecular cation-π

interaction. Further Matthews et al. synthesized thiacalix[4]tube 138 and found that it

has poor binding ability toward K+ ion compared to calix[4]tube.

107 The asymmetric

heterocalix[4]tube 139 (calix[4]-thiacalix[4]tubes) was obtained by condensation of

tosyloxyethoxycalix[4]arene with corresponding thiacalix[4]arene in the presence of

K2CO3 in acetonitrile.108

The complexation of heterocalix[4]tube was controlled by

wider rim substitution of thiacalixarene fragment. The molecular tube 139 with an

adamantine-containing thiacalixarene unit is capable of quantitatively binding

potassium and rubidium cations. The 1,3-alternate calix-thiacalix[4]crown trimers

140a-b bearing crown-5 and crown-6 encapsulate the Cs+ and K

+ ions in the outer

cavities, respectively and the Ag+ ion was found to be entrapped in the central

thiacalix spacer as 1:1 complex. The variable-temperature 1HNMR studies reveal that

the encapsulated Ag+ ion oscillate through the central thiacalix spacer with the aid of

cation-π interactions.

O

O

O

O

O

O

O

RS

R

R

R

O

S

S

S

S

O

O

O

O

S

S

SO

O

O

O

O

O

O

O

O

O

O

O

O

O

O

OO

O

nn

138

137 R = CH2C6H5

140a-b

140a: n=1 140b: n=2

136a: n=0 136b: n=1

136a-b

139: R =

30


OO O

S

OSS S

N N N N

OROR HO

S

OHSS S

N

N

N

N

N

N

N

N

The thiacalix[4]podand 141 having pyridyl groups show high affinity for Ag+

ion.109

The conformational changes of pyridine nitrogen atom from the original

outward orientation against the cavity to the inside orientation toward the

thiacalixarene cavity were observed in the process of Ag+ complexation. Similarly

compounds 142a and 142b having bithiazoyl and bipyridyl groups have best

efficiency for Cu2+

and Ag+ ions.

110

Sykora et al.111

synthesized self-assembled supramolecular networks of 143a-

b formed by the interactions of thiacalix[4]arenes bearing simple alkyl groups on the

narrow rim with silver triflate. The presence of four sulfur atoms enables the

formation of S-Ag-S connections between the individual molecules. These systems

form infinite 1-D coordination polymeric structures in the solid state. Interestingly,

the linear coordination polymers were obtained using both the conformationaly

immobilized and the conformationaly mobile thiacalix[4]arenes, which indicates the

generality of this behaviour in thiacalix[4]arene series.

Csokai et al.112

reported thiacalix[4]arene derivative 144 possessing

dithiacrown ethers and allyloxy-substituted thiacalix[4]arene 145 and studied their

complexation behaviour which shows that the 1,3-alternate conformations are more

effective silver binding agents than those which exist primarily in the cone

conformations. The ditopic receptor 146 possessing two complexation sites and

bearing 1,3-alternate conformation based on thiacalix[4]arene was prepared.113

The

exclusive formation of mononuclear complexes of 1,3-alternate-derivative with Na+,

K+ and Ag

+ ions is of particular interest in regard to a negetive allosteric effect in the

thiacalix[4]arene family. The decomplexation of K+ from the ester sites to form the

Ag+ complex with 1,3-alternate-derivative complex by addition of AgSO3CF3 is the

first example of negative allosteric effect in the thiacalix[4]arene family.

141 142a-b

142a: R =

142b: R =

N NH2C

N

S

N

S

H2C

31


S

OO

OO

SSS

RR

R R

S

OO

OOS SS

SS

N

Oct Oct

S

OO

OO

SSS

S

O O

O O

SS S

N N

OEt

O

OEt

O

Appelhans et al. synthesized cone-type and spherical lysine dendrimers 147 up

to generation 3 based on thiacalix[4]arene core units and used them as molecular

scaffolds for supramolecular host systems.114

The tetraacetate of thiacalix[4]arene

148b shows a high binding affinity for Fe3+

ions by the cone conformers at pH 5.5

compared to calix[4]arene derivative 148a. However interestingly the compound in

1,3-alternate conformation did not bind to any metal ion under similar conditions.115

Iki et al.116

reported chirally modified thiacalix[4]arene 149 with R or S-

phenylethylamine which showed a fair enantioseperation for various analytes

including chiral alcohols, amino acids and amine derivatives.

OHOH O

S

OSS S

NO

HR

NO

HR

OO O

X

OXX

X

HO2CCO2HO O

OHO2CCO2HO

OROR O

S

OSS

S

O NH

Ph

ONH

Ph

Tu et al.117

developed a facile method to prepare size-controllable AuNPs in

aqueous phase by using amphiphilic p-tert-butyl thiacalix[4]arene 150 grafted with

poly(ethylene glycol) monomethyl ether (SCa-MPEG550) as stabilizer and reductant.

During the preparation of AuNPs, the phenolic groups of SCa-MPEG550 150 without

poly(ethylene glycol) chain are oxidized to benzoquinones (SCaQ-MPEG550) 151a-c,

so SCa-MPEG550 acts as reductant of AuNPs. The particle sizes of AuNPs can be

readily controlled by only adjusting the feeding ratio of Au/S. On the other hand,

144 145 146

149

143a: R = CH3

143b: R = C3H7

143a R = CH3

143a-b

148a: X = CH2

148b: X = S

143a R = CH3

148a-b

147

N

N

O

OH

O NO

O

H

H

R =

32


Kozlova et al.118

reported a molecular tecton 152 with S4 symmetry and offering two

sets of coordinating sites i.e. four sulfur atoms and four benzonitrile groups. The

compound 152 in the presence of AgNO3 results in the formation [152.(AgNO3)10]

complex having 3-D coordination network in the crystalline phase resulting from the

mutual interconnection of decanuclear silver nanoclusters and organic tectons. The

important structural features for the organic tecton 152 are close to those observed for

the free tecton.

OHOH HO

S

ORSS

S

R = CH2CH2O(CH2CH2O)12CH2CH2OCH3 R = CH2CH2O(CH2CH2O)12CH2CH2OCH3

OHO O

S

O O

ORSS

S2-n

n

Au

S

OROR

OROR

SSS

R = CH2PhCN

Shamova et al.119

studied the complexation of methyl-glycine-amide

functionalized thiacalix[4]arene 153 with K+ and Ag

+ using density functional theory

(DFT) in the gas phase. Hydrogen bonding of amide hydrogens of podand arms was

found to take place predominantly with the ether oxygens of the same arm rather than

the carbonyls of other arm. The silver cation favour coordination with S atom (for the

cone conformer), N (for one of the 1,3-alternate conformers); the S-coordination

mode is clearly preferred. The stability order cone > 1,3-alternate > paco was found

for the Ag+ complexes. On the other hand, potassium cation favour interaction with

the four carbonyl oxygens of the podand amide arms and the stability order of 1,3-

alternate > cone > paco was found for the K+ complex. For all obtained conformers,

intramolecular hydrogen bonds disfavor complexation, increasing the pre-

organizational energy to be paid.

The ditopic receptors 154 and 155 of thiacalix[4]arene of cone- and 1,3-

alternate conformations, respectively, possessing four 2-pyridyl groups were

synthesized by Yamato et al.120

The single crystal X-ray analysis of tetraamides in

cone conformation show strong intramolecular hydrogen bonding between sulfur

atom on the bridge and NH proton (S---HN), and between the phenolic oxygen and

the NH proton (ArO---HN). These receptors containing pyridine groups showed high

150 152 151a-c

151a: n = 0

151b: n = 1 151b: n = 2

143a R =

CH3

33


affinity toward Ag+ ion complexation and poor affinity towards halide anions.

Another thiacalix[4]arene based ditopic receptor 156121

forms mononuclear

complexes with Li+ and Ag

+ even though the formation of the heterogeneous

dinuclear complexes was expected. Further, they have developed hydrogen-bonding

self-assembly of heterodimeric systems of bis(4-pyridyl) and dicarboxylic acid

derivatives 157 and 158 of thiacalix[4]arene of 1,3-alternate conformation. Although

the values of the dimerization constants are relatively small, the stability of the dimers

is strong enough to overcome only small conformational changes upon complex

formation.

R = -CH2CONHCH3

S

S

S

S

RO

OR

OR

RO

ButBut

ButBut

OROR RO

S

ORSS

S

R =N

NHC-H2C

O

S

OROR

OROR

SSS

R =N

NHC-H2C

O

S

OO

OOS

SS

N N

OO

S

O

O

O

O

S

S

S

N

N

O

OO

O

S

O

O

O

O

S

S

S

N

N

O

OO

O

H

H

S

O

O

O

O

S

S

SO

OO

O

S

O

O

O

OS

S

S

N

N

Ph

H

H

Ph

Stoikov et al.122

reported a series of new p-tert-butylthiacalix[4]arenes

derivatives 159-175 of cone, partial cone, and 1,3-alternate conformations (Table 4)

with o-, m-, p-amido and o-, m-, p-(amidomethyl)pyridine substituents at the narrow

rim. The binding ability of these derivatives was investigated by UV-vis spectroscopy

and found to be selective to recognize the α-hydroxy (glycolic, tartaric) and

dicarboxylic (oxalic, malonic, succinic, fumaric, and maleic) acids.

153 154 155

156 157 158

34


S

OO OOSS

S

R RRR OO OO

SO

O

O

SS

O

S

RO

R O

RO

RO

S

OO

OO

SSS

R R

RR

OO

OO

The chromogenic supramolecular vanadophiles 176a-f123

based on a 1,3-

alternate thiacalix[4]arene were found to show high affinity toward vanadate ions,

attributed to the pre-organization of chelating sites on a stable molecular platform.

These receptors simultaneously coordinate two vanadate ions giving a highly

staggered geometry with almost D2d symmetry. Among various derivatives of 176a-f,

the superiority of 176f may be accredited to the high inductive and mesomeric effects

of the nitro group, which make the N-OH protons more labile, thus facilitating

complex formation. Kundrat et al.124

synthesized molecular tweezers based on

calix[4]arene/thiacalix[4]arene-porphyrin conjugates 177a-b which form 1:1

complexes with C60 and C70 fullerenes in solution while possessing a high selectivity

towards fullerene C70.

Praveen et al.125

synthesized a thiacalix[4]arene derivative 178 of 1,3-alternate

conformation bearing four quinolinoloxy groups which is highly selective for Hg2+

ion showing “on-off” type fluoroionophoric properties. The ligand attained unusual

conformation of a tetra-mercury complex enclosing one Hg2+

ion each in the four

cavities of propyl arms containing quinolinoloxy groups. The fluorogenic receptor

179 having dansyl moiety was used as effective chemosensor for Cd2+

ions in aqueous

medium.126

Further, various thiacalix[4]arene derivatives of mono to tetra-dansyl have

also been synthesized and found to be selective for soft metal ions like Co2+

, Ni2+

and

Cd2+

. The ferrocene-based 1,3-alternate thiacalix[4]arene ditopic receptor 180 have

been synthesized by Guo et al,127

that contains four identical polyether arms

Cone

159-163

Partial Cone

164-169

1,3-alternate

170-175

Cone Partial cone 1,3-alternate R

159 164 170 o-HNPy

160 165 171 m-HNPy

161 166 172 p-HNPy

162 167 173 o-HNCH2Py

163 168 174 m-HNCH2Py

169 175 p-HNCH2Py

Table 4. Thiacalix[4]arenes based receptors 159-175.

35


terminated with ferrocene amide moieties. This redox-active receptor can be used as

an electrochemiacal sensor to recognize both Eu3+

and dihydrogen phosphate (H2PO4-

) ions with a high selectivity.

S

O

O

O

O

S

S

S

N

N

N

N

O

O

O

O

OHOH

R

R

R

R

HO

HO

X

OPrOPr

OPr

Y

Y

Y

Y

OPr

XXX Y=

N HN

NNH-CH=N

S

O

O

O

O

S

S

S

O

O

NO

NO

N

N

OHOH O

S

OSS S

SO2

N(CH3)2

SO2

N(CH3)2

S

O

O

O

OS

S

SO O

OO

O O

O O

NH R

NH

O

RNH

O

R

NH

O

R

O

R= Fe

Thus, from above review we observed that the binding studies of

thiacalix[4]arenes derivatives have been evaluated by solvent extraction method, 1H

NMR spectroscopy and X-ray crystallography. However, the fluorogenic and

chromogenic chemosensors based on thiacalix[4]arene scaffold are much less

explored. Compared to thiacalix[4]arene, the fluorogenic and chromogenic chemistry

of calix[4]arene is much explored towards various analytes (cations, anions and

neutral molecules). Kim et al.128

synthesized a number of calix[4]arenes derivatives

bearing different fluorogenic units.

A calix[4]arene derivative 181 with di(1-pyrenylmethyl)amide-dicarboxylic

acid of 1,3-alternate conformation,129

showed quenching of excimer emission upon

complexation of Pb2+

ions. However, addition of Ca2+

ions to the solution of complex

181-Pb2+

leads to the revival of the excimer fluorescence, leading to formation of an

„On-Off-On‟ molecular switch. The receptor 182130

bearing one 2,3-naphthocrown-6

178 180 179

177a: X = CH2

177b: X = S

177a-b

176a-f

176a: R = H

176b: R = Me

176c: R = OMe

176d: R = Br

176e: R = COOH

176f: R = NO2

36


and two coumarin amide units at the narrow rim in partial-cone conformation of

calix[4]arene showed colorimetric and fluorometric high selectivity for F- and Cs

+

ions. The high fluorescence selectivity toward F- and Cs

+ ions was due to

intramolecular FRET from the naphthalene emission to the coumarin absorption. Kim

et al.131

reported a pyrene-appended fluorescent chemosensor 183 having two

different types of cation binding sites on the narrow rims of a 1,3-alternate

calix[4]arene forms a strong excimer in solution between two pyrene moieties. The

excimer emission of 183 was quenched by Pb2+

, but revived by addition of K+ to the

Pb2+

ligand complex. The metal ion exchange produces an on-off switchable,

fluorescent chemosensor. The computational results showed that the highest occupied

molecular orbital (HOMO) and the lowest unoccupied molecular orbitals (LUMO) of

the two pyrene moieties interact under UV irradiation of 183 and its K+ complex,

while such HOMO-LUMO interactions are absent in the Pb2+

complex.

O O

O O

OH HO

O O

NHHN

O O

O

O

OO

NHO

HN

O

O

OF3C

O O

CF3

OO O

O

O O

O O

O O

O

NHO HN O

O OO O

NH HN

NNHO HN

OOO

H2N

The calix[4]triazacrown 184 bearing primary alkylamine and two pyrene units

reveal a quenched monomer emission because the pendent amine group (-

CH2CH2NH2) which takes part in a PET process: an electron transfer from a lone-pair

electron of the nitrogen atom to two pyrene units.132

When Pb2+

is added to a solution

of 184, the monomer emission increases with quenching in excimer emission due to

conformational changes of the carbonyl bonds (flipping over) as well as to the

participation of the primary amine. In contrast, the addition of Li+ to the ligand 184

causes both monomer and excimer emission to increase, which was attributed to the

CHEF effect. In addition, compound 184 shows a high selectivity for F- ions with

decrease in fluorescence emission via hydrogen bonding between the amide NH of the

triazacrown ring and F- ions.

181 182 183 184

37


The two photon-absorbing chemosensor 185 based on calix[4]arene of 1,3-

alternate conformation undergoes blue-shifted absorption and enhanced fluorescence

with the addition of an Al3+

or Pb2+

.133

Addition of a Pb2+

ion to a solution of 185.K+

enhanced the fluorescence emission due to the allosteric effect induced by the

complexation of K+ with the crown loop. The two-photon processes provide a useful

design strategy for the synthesis of the two-photon sensors for biological applications.

O

O

O

O

O

O

O

HN

O

HN

O

N

CN

NC

N

CN

NC

OHOH OO

HNOO

NH

N

OH OHO O

NHO O

HN

O

N

O

NN

Othman et al.134

reported a monobridged fluorogenic biscalix[4]arene 186

containing pyrene and rhodamine B moieties which was found to be selective for Hg2+

and Al3+

ions. The addition of Hg2+

to a solution of compound 186 resulted in

significantly enhanced fluorescence at λem = 575 nm via FRET-ON from the pyrenyl

excimer to the ring opened rhodamine moiety with excitation at 343 nm. Whereas,

complexation of Al3+

results in strong emission of the pyrenyl excimer but weak

rhodamine emission, suggesting that Al3+

prefers the formation of a pyrenyl excimer

but not the ring-opening of the spirolactam of the rhodamine. Park et al.135

reported

calix[4]arene based fluorescent chemosensor 187 containing triazoles moieties which

showed high selectivity for Cd2+

and Zn2+

ions in a ratiometric manner through an

enhanced monomer and declining excimer emission.

Choi et al.136

reported the behaviour of PCT-based calix[4]crown fluorescent

chemosensors 188 towards transition metal ions (Pb2+

and Cu2+

) and an alkali metal

cation (K+). For the transition metal ions, both monomer and excimer emissions were

quenched due to reverse PET and conformational changes. The addition of K+ ions

results in its encapsulation in the crown-5 ring which induces a more favourable

interaction between the HOMO and LUMO, resulting in stronger excimer formation.

The addition of K+ ions to the 188.Pb

2+ complex, there was revival of fluorescence

emission indicating the metal ion exchange process between K+ and Pb

2+ ion.

185 186

38


OO OHOH

N

NN

N

N N

O O

O O

O O

O

NHO HN O

O OO O

O O O O

N NN N

N NNN

OO OHOH

NN

N

OHBut

N

N N

N

HO But

N

The fluorescent chemosensor 189137

based on calix[4]arene bearing four

iminoquinoline subunits on the wider rim showed a remarkable enhanced fluorescent

intensity in the presence of Cu2+

ion and a high selectivity toward Cu2+

ion over a

wide range of tested metal ions. Pathak et al.138

developed a fluorescence turn-on

receptor 190 based on triazole linked calix[4]arene for selective recognition of Zn2+

in aqueous-methanolic HEPES buffer. Further, the receptor 190 showed its utility for

sensing Zn2+

in blood serum milieu and in the presence of albumins.

OO OO

HN OO NH

S S OOO O

N(CH3)2N(CH3)2

O

OBu

OBu O

OO NHNH

S S OOO O

N(CH3)2N(CH3)2

OO OO

HN OONH

R R

HNOO NH

R R

O O

O O

NO2 NO2

O2N NO2

N

S OO

N

SO O

N

SO O

N

S OO

Talanova et al. reported fluorogenic receptors 191 and 192 possessing

sulphonamide moieties based on calix[4]arene of cone and partial-cone

conformations. Receptor 191 showed fluorogenic detection of Hg2+

ions in acidic

aqueous solution even in the presence of 100-fold excess of various other metal

ions,139

while receptor 192 of partial-cone conformation showed fluorescence

enhancement in the presence of Pb2+

ions with a lower detection limit of 2.5 ppb.140

The tetra-dansyl derivative of calix[4]arene 193 reported by Metivier et al.141

showed

ratiometric selectivity towards Pb2+

ions.142

Another tetra-dansyl appended

calix[4]arene derivative 194 of 1,3-alternate conformation reported by Pandey et

187 188 189 190

191 192 194

193

S

O

O

N

R =

39


al.143

showed high selectivity and adequate reversibility for Hg2+

ions. Compared to

cone conformation of dansyl-appended calix[4]arenes, the derivative 194 of 1,3-

alternate conformation showed high selectivity for Hg2+

ions. The disubstituted

dansyl derivative 195 grafted on a large pore mesoporous silica material, showed an

optical signaling of Hg2+

in aqueous solution, with reversible binding of the cation.144

A triazole appended calix[4]crown derivative 196145

of 1,3-alternate

conformation synthesized using click chemistry shows a fluorescence quenching in

presence of Pb2+

, Hg2+

, Cu2+

and Cr3+

ions. This fluorescence quenching is attributed

to the reverse PET from anthracene unit to the triazole group. However, revival of

fluorescence emission from the strongly quenched 196-Pb2+

complex was observed

on addition of K+ ions showing „On-Off‟ switching phenomenon. Chen et al.

146

reported calix[4]arene based azacrown 197 substituted with a lariat arm carrying a

dansylamide fluorophore. Receptor 197 showed a selective and sensitive sensing of

Hg2+

ions based on a fluorescence quenching in presence of metal ion due to the

excited state charge transfer from the dansyl moiety to the Hg2+

ions. Another

azacrown modified derivative 198 reported by Kim et al.147

showed selective

quenching of pyrene fluorescence in presence of Hg2+

ions.

OO OO

(CH2)n(CH2)nHN

OONH

S S OO

O O

N N

Si Si

OEtEtO

EtO

OEtOEtEtO

O

OO

O

O

OO

N NN N

N N

OHOH OO

NH

S

N

O NH

N

HNO

O

O

OHOH OO

N N

OHNO NH

For the last few years, fluorescent imaging using various fluorescent probes

provides a highly sensitive, efficient and temporal analysis of cells148

and is widely

used in the field of biology and physiology. The development of optical fluorescent

probes of a particular analyte for fluorescent imaging help to map the molecular

details of biological processes like metal ion transport, homeostasis and participation

in disease pathology.149

The optical detection of metal ions in living organisms offers

great significance to study their site of action and physiological functions.150

The

biological detection of particular analyte by fluorescent imaging can provide direct

information on their spatiotemporal distributions in living systems.

195: n = 32 196 197 198

40


Komatsu et al.151

reported the simultaneous imaging of intracellular Ca2+

and

Mg2+

ions with a novel single-molecular multi-fluorescent probe 199 due to the

different optical response patterns of the two selective binding sites. Upon

complexation to Ca2+

ions, probe 199 shows a 45 nm blue shift in absorbance and a 5

nm blue shift in the fluorescence spectrum. For Mg2+

ions, a 21 nm red shift in

absorbance and a 5 nm red shift in fluorescence occurred. The probe 199 was

biologically evaluated by applying it into differentiated PC12 cells. Yang et al.152

reported a multi-signaling sensor 200 based on rhodamine B with a ferrocene

substituent which shows extreme selectivity for Hg2+

ions over other metal ions.

Multi-signaling changes were observed through UV/vis absorption, fluorescence

emission, and electrochemical measurements. The confocal laser scanning

microscopy experiments have shown that 200 can be used to detect Hg2+

ions in living

cells and map its subcellular distration.

A rhodamine-based reversible chemosensor 201153

binds to Hg2+

and Cu2+

ions in aqueous methanol solution with detectable change in color and different

fluorescence output signals. Further, this sensor 201 could detect the Hg2+

ion

adsorbed on the cell surface of the microorganism such as Pseudomonas putida and

thus could be useful for determining the amount of Hg2+

ions that could enter in the

food chain affecting human beings along with phytoplanktons and zooplanktons.

Another rhodamine based chemosensor 202154

possessing dansyl moiety has been

utilized as ratiometric sensor for detection of Hg2+

ions in aqueous solution using

resonance energy transfer mechanism. The receptor 202 could be used as staining

agent for detection of Hg2+

ions uptake in bacteria living cells such as Pseudomonas

putida.

O

HOOC

OO

N

COOH

COOH

O

F

NHOOC

HOOCN

O

ON N

N

O

N

Fe

ONH

NH

N

O

N

HOOC

ON NH

N

O

N

N

S OO

S

The hypersensitive water-soluble fluorescent probe 203155

can selectively

detect low levels of Hg2+

ions in buffered aqueous solution with high affinity and

turn-on response. Further investigations in living cells demonstrated the potential

199 200 201 202

41


applications of this novel probe for the study of the toxicity or bioactivity of Hg2+

ions

in living cells. The quinoline-based fluorescent probes 204a-b displays high

selectivity and sensitvity for Zn2+

ions in a neutral buffer aqueous solution.156

The

probes 204a-b exhibits 14-fold fluorescence enhancement in response to Zn2+

ions

which is favourable toward biological applications. The two-photon imaging of

probes 204a-b showed good cell permeability and efficient detection of Zn2+

ions in

living cells. A rhodamine based thiosemicarbazide probe 205157

which reacts

irreversibly with methylmercury via a desulfurization reaction, can detect

methylmercury with high sensitivity in aqueous media. The fluorescent imaging of

HeLa cells and zebrafish demonstrated the detection and real-time monitoring of

methylmercury in living cells and organisms.

N

SO

O

NH

O

OHN

NN

RO

N

N

ONH

NH

N

O

HN

NH

S

OO O

NH3+Cl--Cl+H3N

-Cl+H3N NH3+Cl-

O

HN

NO

N

O2N

O NH

NH

N

S

O

N

N

N O

N

OO O

N

N N N

O

N

N

NO

O NN

N

O

O HN

HN

HN

OO

O

HN NO

O

O O

O

Fe3O4 n

Lalor et al.158

reported the cellular uptake processes and cellular fate for

nitrobenzofurazan derivative of calix[4]arene 206. The fluorescent imaging of this

calix[4]arene derivative showed accumulation of the probe within the cell cytoplasm.

The rhodamine based fluorescent probe 207 possessing thiol and alkyne moieties

have been synthesized by Lin et al.159

The probe exhibits large fluorescence

enhancement, high selectivity and low detection limit for Hg2+

ions based on the

interactions of Hg2+

to both thiol and alkyne moieties in a probe 207. Furthermore,

203 206 205

208 207 209

204a-b

204a: R = CH3

204b: R = C12H25

42


receptor 207 demonstrates its high utility for detection of Hg2+

ions by fluorescent

imaging in the living cells.

The cryptand–rhodamine conjugated chemodosimeter 208 reported by Jana et

al.160

can detect Hg2+

ions in aqueous medium selectively at ppb level in the presence

of other biologically relevant metal ions. This system also shows a good viability in

living cells imaging study (HEK 293 cell line) due to its greater extent of cell

permeability that arises from its adjustable amphiphilic nature.

Wang et al.161

reported a nanoparticle conjugate of Fe3O4-Rh6G-LEDA 209

and demonstrates its high selectivity for detecting Fe3+

ions among various metal ions

in water with the detection limits reaching as low as 2 ppb. The sensitive detection of

Fe3+

ions by the NP conjugate is further demonstrated in HeLa cells indicating the

potential applications of NP conjugate 209 in the biological monitoring and tracking

of iron.

1.6.2 Thiacalix[4]arene based metal complexes

During the last few years, the high-nuclearity coordination clusters of

transition metal cations have been receiving growing attention due to their interesting

electronic and magnetic properties which contribute to their potential as

nanoelectronic components, metalloenzyme models, nanoscale catalysts, and

molecular magnets.162

Among various scaffold, calixarenes with hetero-atoms in the

scaffold and on the rims are excellent candidates as ligands for making multinuclear

metal complexes.163

Thiacalix[4]arene, possessing four phenoxyl groups and four

bridging sulfur atoms, the sulfonyl and sulfinyl derivatives give polynuclear

complexes with most transition metal ions. Further these have been proved to be good

multidentate ligands in constructing polynuclear complexes.164

Such macrocyclic π-

rich ligands may hold efficient energy-transfer properties for the luminescent

materials and the proper orbitals for the construction of metal complexes.

The sulfonyl-based ligands 210a and 210b, synthesized by Horiuchi et al,165

form luminescent 1:1 complexes with Tb(III) ion having higher luminescent quantum

yield (Φ = 0.29 and 0.28, respectively) than 1:1 complexes of the corresponding

thiacalix[4]arene-based di- and tetracarboxylate ligands (Φ = 0.04 and 0.003,

respectively), implying higher efficiency of sulfonyl ligands than those of thia ligands

in the energy transfer process.

43


OOO

X

O

XX X

OO O O

OOO

X

O

XX X

OO

OO

OO O O

TbIII

TbIII

OS

S

OO

OSS

Ti

ClCl

Ti

ClCl

OHOH HO

R

S

R R R

OHSS S

Mono- and dinuclear titanium complexes of p-tert-butylthiacalix[4]arene

211166

were applied as a catalyst for [2+2+2] cycloaddition of terminal alkynes and

found to have high catalytic activity and regioselectivity toward 1,3,5-trisubstituted

benzenes over 1,2,4-trisubstituted isomers. The regioselectivity was due to steric

effect of the thiacalix[4]arene skeleton and the coordination of the bridging sulfur

atom to the titanium centre.

The tetranuclear complexes of de-tert-butylated thiacalix[4]arene 3 and p-

phenylthiacalix[4]arene 212 with lanthanide metals (Ln = TbIII

, DyIII

) demonstrated

an efficient luminescent and magnetic properties.167

All the frameworks obtained can

be formulated as [LnIII

4(212/3)2(μ4-OH)Cl3(CH3OH)2(H2O)3], and some methanol

and water solvent molecules are occupied in the interstices. The compounds showed a

sandwich like unit constructed by two tail-to-tail thiacalixarene molecules and a

planar tetragonal (μ4-OH)Ln4 cluster. There was an effective ligand-to-LnIII

energy

transfer for these compounds and 212 is a more efficient “antenna” than 3. The DyIII

compounds exhibit slow magnetic relaxation behaviour of single-molecule magnet

nature. The replacement of the t-Bu group by a p-phenyl group at the wider rim of

thiacalix[4]arene leads to different extended structures and a kind of multifunctional

material with photoluminescence and small molecular magnet (SMM) like properties.

Bi et al.168

reported a novel complex of {Co32} cluster core capped by six p-

tert-butylthiacalix[4]arene 11 molecules and appear as a sodalite CoII

24 cage

encapsulating a CoIII

8 cube. The thiacalixarenes capping six faces of a hexahedron

exhibit a unique arrangement for the thiacalixarenes. In two isomers, the

thiacalixarene-capped {Co32} spherical units are arranged into a body-centered cubic

lattice, while in the third isomer, they are assembled in a cubic closest packing

pattern.

The single-crystal x-ray diffraction studies of [K(11·3H)]·2MeOH complex,

obtained from the reaction of p-tert-butylthiacalix[4]arene 11 with KH, shows the

1

9

2

0

210a: X = SO2 210b: X = SO2 3: R = H

212: R = Ph 211

44


formation of dimers.169

One of the dimers was formed by a hydrophobic interaction

between each tert-Bu group of 11·3H and the cavity of another 11·3H in the crystal

state. The other dimer made metal coordination S···K···(O,S,O) between

neighbouring 11·3H and potassium ions. In the overall structure, this complex

indicates a nonporous structure and the adsorption capabilities toward gaseous organic

molecules are studied.

Amirov et al.170

reported the gadolinium (III) complexes possessing high

relaxivity with various tetraacid stereoisomers based on p-tert-butylthiacalix[4]arene

213-215 in micellar solutions of non-ionic surfactants (A-C). The acid-base properties

of individual isomers of the ligand were studied by pH-metric titration and UV

spectroscopy and revealed the influence of the spatial arrangement of the functional

groups in the p-tert-butylthiacalix[4]arene stereoisomers substituted by carboxy

groups at the narrow rim on the ability to bind the Gd3+

ions to form water soluble

complexes possessing high relaxivity. In addition, he evaluated the influence of type

and concentration of the nonionic surfactant in solution on the degree of binding of

the paramagnetic probe and relaxivity of gadolinium solutions containing calixarene-

surfactant mixed aggregates.

S

OO

OOS

SS

OH HO

HOOH

OO

OO

S

OO OOSS S

OH HOHOOH OO OO

SO

O

O

SS

OS

OHO

HO O

OHO OHO

O CH2CO2CnH2n+1

OHO(CH2CH2O)yH

Hx(OH2CH2C)O

x + y = 20; n = 11 (Tween-20), 15 (Tween-40), 17 (Tween-60)

Me O(CH2CH2O)23H

O(CH2CH2O)nH

Me

Me

ButH2C

n = 10 (TritonX-100), 40 (TritonX-405)

A B

C

Chen et al.171

demonstrated the formation of a chiral Kagome network

structure (A Kagome lattice,172

also known as trihexagonal tiling, represents a

periodic arrangement of interlaced triangles such that each point where two triangles

cross has four neighboring points) using thiacalix[4]arene tetrasulfonate (TCAS) 216

as a building block at an aqueous/Au (111) interface with potential control. The

213

214

215

45


interesting feature of the system was that the building block of the chiral Kagome

network was a structure-complicated supramolecule calixarene rather than simple

planar or near-planar organic molecules. It opens the possibility to construct a 2D

nanoporous network by various functional supramolecules. Further, the TCAS can

interact with guest molecules through hydrogen bonding as well as

hydrophilic/hydrophobic and π-π stacking interaction, a plethora of host-guest

complexes could be integrated into the Kagome network. The construction of a chiral

cavity array in aqueous media would facilitate single molecular recognition with

biological active chiral molecules. Liu et al evaluated the stability constants (Ka) and

thermodynamic parameters (ΔG°, ΔH°, and TΔS°) for 1:1 complexation of water-

soluble thiacalix[4]arene 216 / calix[4]arene 217 with pyridine and their methylated

derivative by means of isothermal titrations calorimetry at pH 2.0 and 7.2 at

298.15K.173

The results obtained show that sulfonatocalixarenes afford stronger

binding ability toward pyridine guests at pH 2.0, attributable to the positive

electrostatic interactions and the more extensive desolvation effects, but present

higher molecular selectivity at pH 7.2 owing to the strengthened C -H... interactions.

OHOH HO

SO3-Na

S

Na-O3SNa-O3S SO3-Na

OHSS S

OHOH HO

SO3-

X

-O3S SO3- SO3

-

OHXX X

O-O- -O

SO3-

S

-O3S-O3S SO3

-

O- SS S

O-O-

O-

SO3-

S

-O3S -O3S SO3-

O-

SS S

TbAg Ag

N

HN

N

NH

NCH3

NCH3

NH3C

NH3C

TMPyP

+

++

+

The intercalation behaviour of water-soluble tetrasodium p-

sulfonatothiacalix[4]-arene (TCAS) 216 was studied by intercalating it into layered

double hydroxides (LDH).174

Utilizing the osmotic swelling of LDH in formamide,

the bulky thiacalix[4]arene anion is introduced, leading to the recovery of LDH

layers, and the hexagonal prism morphology. The osmotic swelling/restoration

method could be a useful technique to prepare regularly stacked layered compounds

with large bio- or organic molecules as guests in the interlayer. Further, Huang et

al.175

intercalated water-soluble-tetrasodium p-sulfonatothiacalix[4]arene (TCAS) 216

into MgAl-LDH using an osmotic swelling/restoration reaction of the LDH in

TCAS

216

219

216: X = S 217: X = CH2

218

46


formamide. The arrangement of TCAS in the interlayer can be controlled through

adjusting the area per unit charge (Scharge) of TCAS. When Scharge (TCAS)<Scharge

(LDH), monolayer (basal spacing, dbasal, 1.30 nm) and alternating “up-down”

antiparallel (dbasal, 1.54 and 1.45 nm) arrangements were obtained. When Scharge of

TCAS was increased by forming an Ag+ complex, bilayer arrangement (dbasal, 2.12

nm) of TCAS (Ag) was formed. This swelling/restoration reaction took place, and the

composites retained the morphology of the LDH precursor. The thermal stability of

TCAS in the composites was remarkably enhanced, and the “up-down” antiparallel

arrangement of TCAS had the highest increase of thermal stability.

The photophysical properties of supramolecular complex of thiacalix[4]arene-

p-sulfonate (TCAS) 218176

with Tb(III), and Ag(I) ions in aqueous solution was found

to exhibit energy-transfer luminescence with an exceptionally long lifetime (4.6 ms).

The crystal structure of these complexes indicate that two TCAS ligands are linked by

two S-Ag(I)-S linkages to adopt a double-cone supramolecular structure.

Odo et al.177

reported a new water-insoluble Fe3+

-TCAS (216)/TMPyP (219)

complex of tetraanionic Fe(III)-thiacalix[4]arenetetrasulfonate (Fe3+

-TCAS) with

tetracationic tetrakis(1-methylpyridinium-4-yl)porphine (TMPyP) 219 via ionic

interaction. The peroxidase-like catalytic activity of the Fe3+

-TCAS/TMPyP complex

was investigated based on the dye formation reaction by oxidation of 4-

aminoantipyrine and phenol with H2O2 catalyzed by peroxidase. This Fe3+

-

TCAS/TMPyP complex showed the highest activity at pH 5.5 acetate buffer solutions,

and it was applied to the photometric determination of trace amounts of H2O2.

Moreover, the method using glucoseoxidase and the Fe3+

-TCAS/TMPyP complex was

applied to the determination of glucose. The Fe3+

-TCAS/TMPyP complex can be

applied to a practical sample, such as blood or urine, as an analytical reagent for the

photometric determination of H2O2 in place of peroxidase.

A heterogeneous one-step self-assembly of Ag+, Tb

3+, and tetrasodium p-

sulfonatothiacalix[4]arene (TCAS) 216 was reported by Tanaka et al.178

of which the

donor atoms S and O showed high selectivity toward Ag+ and Tb

3+ ions, respectively.

The cage structure of ternary complex, [Ag4Tb(tcas)2dmf2]9-

was formed by the one-

step heterogeneous self-assembly of Ag+ and Tb

3+ ions with the TCAS ligands. The

Tb3+

ion was encapsulated in an octa-oxygen cube, it was shielded from solvent

molecules such as water and DMF, which has advantage of construction of a highly

luminescent environment for a lanthanide (III).

47


The mononuclear 220 and dinuclear complexes 221 of p-

sulfonatothiacalix[4]arene (TCAS) 216 with Ce(IV) was synthesized by Matsumiya et

al.179

The dinuclear Ce(IV) complex 221 promoted the hydrolysis of p-nitrophenyl

phosphate with a turnover frequency of 6.8 h-1

at 50 °C, showing fourfold higher

activity than the mononuclear complex. The dinuclear complex was readily

immobilized onto an antibody by simply mixing them in water, and its phosphatase-

like activity was applied to the color-developing reaction in immunoassay. The model

assay using an antibody labelled with the dinuclear complex allowed the detection of

as little as 10 ng mL-1

of a tumor marker, Bence-Jones protein, in a 96-well microtiter

plate format.

Mononuclear complex

S

S

S

S-O3S

SO3-

SO3-

-O3S

O-

HO

HO

O-M S

S

S

S-O3S

SO3-

SO3-

-O3S

O-

-O

-O

O-M M

Dinuclear complex

O-O- HO

SO3-

S

-O3S SO3- SO3

-

OHSS S

OHOH -O

SO3-

S

-O3S SO3-

SO3-

O-

SS S

Ag Ag TbTb

O

H

HO

H

H

O H

H

O

H

H

Iki et al.180

reported an assembled supramolecular structure 222 consisting of

multidentate and photon-absorbing p-sulfonatothiacalix[4]arene (TCAS) 216,

luminescent TbIII

and analyte AgI, with linear coordination geometry that is capable of

sensing AgI ions at nanomolar concentrations. Two thiacalix[4]arene ligands are

linked by analyte AgI ions and then coordinate to Tb

III ions to form a luminescent

ternary complex, AgI2.Tb

III2.TCAS2, enabling the nanomolar detection of Ag

I. The

sensing function of assembled structure originates from the supramolecular nature of

complex 222, and not from TCAS and TbIII

individually. Thus, the complex 222 truly

demonstrates the „„supramolecular strategy.‟‟

Two isomorphous complexes of p-sulfonatothiacalix[4]arene (TCAS) 216,

cobalt(II) nitrate or zinc(II) nitrate and methylviologen dihexafluorophosphate

(MV(PF6)2) , {[M(H2O)6]2+

[MV]2+

[(MV)2M2(H2O)4(216)2]4-

}·14H2O (M= Co; Zn)

form a dimer with Ci symmetry through the coordination of sulfonate groups.181

The

220

221

222

48


dimers further extend their structures through second-sphere coordination and π- π

stacking interactions into three-dimension nets.

Buccella et al.182

reported the mononuclear Mo and W complexes 223a-b, 224

and 225a-b of p-tert-butylthiacalix[4]arene 11, and p-tert-

butyltetrasulfonylcalix[4]arene (TCAS) 216. The comparison with the related

calix[4]arene complexes indicates that the chemistry of the system is strongly

influenced by the nature of the calixarene linker, i.e., CH2, S, and SO2. For example,

in contrast to the methylene-bridged calixarene system, the thiacalixarene and

sulfonylcalixarene systems readily coordinate a second metal center to form homo-

and heterodinuclear complexes 223-225. Of most interest, incorporation of Ni into

complex 223a using Ni(PMe3)4 results in cleavage of a C-S bond to give 226, an

observation that is of relevance to the role that Ni plays in hydrodesulfurization

catalysis.

S

OO OOSS S

Mo

Me3P PMe3

PMe3

H

H

HH

S

OO OOSS S

Mo

Me3P PMe3

PMe3

HH

hv

H2

Mo

Me3PPMe3

PMe3

O

SX

OHOH

OXS

O

O

O

O

H+

hv

H2

Mo

Me3P

PMe3

PMe3

OS

X

OHOH

OXS

O

OO

O

HH

Mo

Me3P

PMe3

PMe3

OS

X

OHOH

OXS

O

OO

O

S

OO OS

S

Mo

Me3P PMe3

PMe3

H

H

HO

S

Ni

PMe3Me3P

1.6.3 (Thia)calix[4]arene based receptors for anions

Anion recognition chemistry has emerged as an exciting research field in

supramolecular chemistry in recent years owing to the biological and environmental

relevance of anions.183

The anion recognition has been a great challenge since anion

complexation with the receptor is quite different from that for metal cations because

of their varying size, shape and charge, and pH-dependent species. However,

significant progress has been made in the development of anion receptors using

223a

223b

224: X = SO2

225a: X = SO2

225b: X = SO2

226

49


different molecular scaffolds.184

The recognition of anion has been achieved using

different artificial receptors such as neutral anion receptors (amide, urea/thiourea,

benzimidazole, pyrrole, alcohol and phenol) containing different hydrogen bond

donors and positively charged anion receptors (comprising of functional moieties like

ammonium, guanidinium, phosphonium, metal-complexes and pyridinium). Various

anions such as fluoride, cyanide, sulphate and phosphate play many key roles in

biological systems.185

Therefore selective recognition of particular anions is of

considerable interest. Among various scaffolds, (thia)calix[4]arene scaffold186

has

also been utilized for the design and synthesis of anion receptors bearing different

binding moieties such as amide, (thio)urea and various other neutral/ electrostatic

groups. A brief review of anion receptors based on (thia)calix[4]arene scaffold is

reviewed below.

Xu et al.187

reported a F- ion selective calix[4]arene based fluorogenic receptor

227 which binds through NH groups of napthalimide moiety. Liu et al.188

have

appended various anion sensing moieties with chromogenic and fluorogenic reporters

to calix[4]arene-1,3-diamide derivatives with a chiral amino acids in some cases

providing chiral recognition features. One such derivative 228189

shows chromogenic

sensing towards enantiomers of α-phenylglycinate anion and is found to form a 1:1

hydrogen bonded complex with a chiral discrimination of both the enantiomers.

OO OHOH

N OO

NH NH

OROR OO

NH

NH

CH

O

R

O

NH

NHO

HN

HN

HC

O

R

O

HN

HNO

NO2NO2

X

OO OOXX X

HN

O

HNNH

ONH

NH HNNH

NH

Y

O O

NH HNY Y

HN

HNY

R R R R

O O

NN

OH OH OO

HN NH

OHNO NH

O2N

NO2

NO2

NO2

Quinlan et al.190

reported calix[4]arene derivatives 229a-b possessing amido-

urea and p-nitrophenyl group for chromogenic recognition of anions such as

229a: R= NO2, X=CH2, Y=O 229b: R=H, X=CH2, Y=O

227 228 229a-c 230

50


pyrophosphate and fluoride. Chawla et al.191

reported 2,4-dinitrophenylsemicarbazone

derivative 230 of calix[4]arene for chromogenic recognition of fluoride ions.

Kim et al.192

synthesized various calix[4]arene based derivatives containing

pyrene moieties 231-233 for colorimetric and fluorometric sensing of anions. The

binding site of 231 and 232 for anions could be differentiated based on the acidity of

the compounds and the H-bonding patterns. The fluoride anion bound to the amide

groups (-NHs) of 231 and to the hydroxyl protons (-OHs) of 232. The addition of F- to

the solution of 231 changes the characteristic excimer emission peak at 480 nm and

forms a new emission peak at 460 nm (static excimer). Contrary to 231, the addition

of F- to the solution of 232 changes the characteristic absorption spectrum. On the

other hand, the addition of F- to the solution of 233 causes a red shift of its absorption

band to 400 nm (Δλ = 54 nm) and a blue shift of the excimer emission to 470 nm (Δλ

= 12 nm) together with enhanced fluorescence intensity. The blue-shifted excimer

emission is attributed to a static excimer formed in the ground state between two

pyrene units.

OHOHO

N

O

NHO HN O

N

NO2

N

N

NO2

OHOHO

N

O

NHO HN O

N

NO2

NN

NO2

O O

O O

NHO HN O

O OO O

HNNH

HN

O

NH

O

NO2 NO2

Lang et al.193

reported a chromogenic receptor 234 based on calix[4]arene

possessing ureido moieties for detection of spherical and non-spherical anions such as

NO3-

and BzO-. The stoichiometry of complexation depends on the substitution

pattern (distal vs proximal) and anion concentration. While the distally substituted

receptor forms 1:1 complexes with anions, the corresponding proximal derivative

prefers the 2:1 stoichiometry (calixarene:anion) under identical conditions. Miao et

al.194

reported a bridged fluorescent calix[4]arene 235 with 1,8-diaminoanthracene

and glycine at the wider rim. The compound 235 showed good selectivity for

recognition for AcO- over other anions via a PET process due to the formation of

hydrogen bonds between CONH, 9-H (of anthracene) and anions.

231 232 233 234

51


Schazmann et al.195

reported a pyrene-appended tetra-substituted compound

236 based on calix[4]arene of 1,3-alternate conformation bearing neutral two-site

urea functional groups for chloride recognition. The addition of chloride to receptor

236 leads to ratiometric response with quenching of excimer emission and

simultaneous increase in the monomer emission. The receptor 236 has suitability and

advantages of ratiometric optical response for chloride ions even in the aqueous

media. Chawla et al.196

synthesized many neutral calix[4]arene receptors 237a-d

(Table 5) with hydrazone functions at their narrow rim which exhibit a prominent

„naked-eye‟ colour change with significant bathochromic shifts when interacted with

fluoride ions. Among these receptors, 237b exhibits a selective binding with fluoride

ions via H-bond interactions in preference to other ions and elicits a distinct colour

change from yellow to dark purple through efficient deprotonation.

O OO O

O O O O

NH

ONH HN

OHN

O

O

OO

OO

HNNH

HNO

NHO

HNNH

HNO

NHO

OO

(H2C)3 (CH2)3

OHOH

O O

N

NH

R1

R2

XN

HN

R1

R2

X

Zlatuskova et al.197

reported the first example of anion receptors 238a-b in the

thiacalixarene series possessing mixed amido-urea/thiourea funtionalities which

exhibited a competitive anion/ cation complexation of Cl- and K

+ ions. Further, they

reported198

regioselective ipso-nitration of tert-butylthiacalix[4]arene-tetrasulfone for

the construction of thiacalix[4]arene derivatives 239 and 240a-c bearing arylureido

functions on the wider rim of cone and 1,3-alternate conformation. The pre-

organization of ureido units leads to anion receptors with good complexation ability

toward selected anions of various geometries. The thiacalix[4]arene derivative

showed better complexation ability compared to calix[4]arene for these anions even in

highly polar solvent, such as DMSO.

235 236 237a-d

Compound No

X R1 R2

237a H H H

237b H H NO2

237c H NO2 NO2

237d CH3 H NO2

Table 5. Thiacalix[4]arene based

amide receptors 237a-d.

52


OO O

S

OSS S

HN O

NH

NH

X

NHO

HN

HNX

NHO

HN

HN

X

HNO

NH

NHX

X

OO

OOX XX

NH

NH

OHN

HN

O

H3C CH3

-H3C CH3

CH3CH3

R

X

OO HO

HN

OHXX X

HN

O

Pr Pr

R

NH

NH

O

1.6.4 Development of molecular switches and logic devices

Another significant application of supramolecular chemistry is its use in

molecular computing199

based on chemical reactions performed either in solution or at

functionalised interfaces. Currently used computers and other electronic digital

devices are based on monolithic semiconductor structures fabricated on the surface of

silicon wafers.200

All these devices use binary logic for information transmission,

processing, and storage, and utilize electric signals as information carriers. All the

information is encoded in series of zeros and ones, represented as low and high

potential values. Various logic gates such as OR, AND, XOR, INH, NOR, NAND and

XNOR gates201

(Table 6 & 7) are the basic elements for processing information whose

output (0 or 1) depends on input conditions. The data introduced into a computer are

elaborated through a sequential integration of logic operations and converted into a

specific output. The dimensions of these communicating components of logic circuits

continue to be reduced to miniaturization which permits the assembly of integrated

circuits and faster processors.202

The conventional silicon based devices have

limitation of their miniaturization down to the nanoscale.202

Therefore, the

development of materials for information storage and retrieval at the molecular level

is promising choice for this limitation.203

The idea of computation at the molecular

level was first mentioned by Richard Feynman in 1959.204

Vincenzo Balzani was the

first to report the molecular machines based on molecular recognition and self-

assembly in 1992.205

After one year, the first molecular logic gate was reported by A.

Prasanna de Silva based on molecular recognition of target molecules using

fluorescent probes and introduced Binary information processing in the chemical

239: X=SO2

238a: X=O 238b: X=S

238a-b

240a: X=S, R = Me 240b: X=CH2, R = Me 240c: X=CH2, R = NO2

240a-c

53


system.206

The molecular logic gates and other devices were controlled exclusively by

chemical inputs, while the output was observed as changes in fluorescence and

absorption spectra. Thereafter, the scientists have developed keen interest in

molecular computing which is an attractive research subarea of unconventional

computing,199

involving integration of molecular information processes using various

Boolean logic operations (OR, AND, XOR, INH, NOR, NAND and XNOR gates) at

the molecular level. The molecular information processes are related to the integration

and processing of binary data of microprocessor systems.207

The optical sensing of

specific analyte and its integration into molecular level devices such as logic gates and

molecular switches have stimulated interest in the development of molecular

electronic and photonic devices for information processing, sensing and

computation.208

The first molecular logic gate formulated was AND logic gate by de Silva et

al.206

based on receptor 241 comprised of cyanoanthryl fluorophore, azacrown cation

receptor, and the tertiary amino group (proton acceptor). The binding of sodium ions

within the azacrown does not influence the luminescence of the compound as PET

Output

Input

OR AND XOR INH NOR NAND XNOR

0 0 0 0 0 0 1 1 1

0 1 1 0 1 1 0 1 0

1 0 1 0 1 0 0 1 0

1 1 1 1 0 0 0 0 1

Table 7. Truth table for two inputs logic gates.

Table 6. Truth table for single input logic gates.

Output

Input

YES

NOT

0 0 1

1 1 0

54


from amine can efficiently quench the fluorescence. Only simultaneous binding of

sodium ions and protons prohibits PET and switches the fluorescence on. The receptor

242 showed same behaviour of independent binding of protons and alkali metal cation

which results in operation of AND gate. This is the first reported computational

chemical system confined to the nanometer scale objects.209

CNN

OO

OO

O

OO

OO

O

N

O

N

N

O-

The pyrene based receptor 243 containing nitroxide group conjugated on

imidazole ring showed 100-fold increase of fluorescence intensity with the addition of

trifluoroacetic acid and cysteine which result in the formulation of AND gate.210

The

receptor 244211

containing three carboxylate groups bind to magnesium and calcium

ions. This non-selectivity constitutes the basis of OR operation based on the PET

phenomenon. The binding with metal ions results in rearrangement of electronic

structure of compound 244 and fluorescence of the receptor gets switched on. The

receptor 245 also undergoes cation-induced rearrangement upon binding of sodium

ions which bound to the polyether chains, while Hg2+

bounds to the bipyridine unit.

Irrespective of the cation, the molecule undergoes the same guest-enforced

rearrangement, which greatly reduces the distance between two anthryl units and

allows photoinduced dimerization.212

The ditopic binding leads to formulation of OR

gate.

N

NN

CN

NC

O

HO

HO

OH

O

O

O

N

N O O

O O

NO

N O OO

NN

The compounds 246 and 247 show pH-controlled PET processes which form

the basis of XOR gates.213

The XOR gate requires a chemical system that responds to

two different stimuli in such a way that one of these two stimuli should switch on the

241

242

243

244

245

246

247

55


gate, while concomitant presence of both triggering molecules should leave the

system in the OFF state. First protonation of compounds 246 and 247, which occurs at

more basic aliphatic amine group, switches the fluorescence on due to inhibition of

the PET process, while the second protonation at pyridine moiety switches the

fluorescence off by enabling the second PET process involving the pyridinium cation.

A ditopic receptor 248 based on isoquinoline N-oxide with an attached benzo-

15-crown-5 receptor perform the operation of INHIBIT gate (INH) which is a

concatenation of AND and NOT gates.214

Molecules based on this framework show

dual fluorescence from locally excited and charge transfer states involving the

benzocrown moiety. Charge-transfer fluorescence is observed only in the case of the

protonated N-oxide moiety. Binding of cations by crown ether results in a decrease of

HOMO energy of the donor, and CT fluorescence is not observed.

OO

OO

O

N+

-O

N

O

O

N

NN

NN

N

N

de Sousa et al.215

reported 1,8-naphthalimide derivative 249 which shows very

weak fluorescence because of efficient PET quenching. The interaction of compound

249 with Eu3+

ions results in stronger luminescence of the naphthalimide due to

inhibition of PET. However, in the presence of oxygen, no red europium

luminescence was observed. Therefore, compound 249 regarded as chemically driven

INH gate with Eu3+

and O2 inputs and red luminescence as output. The receptor 250

and 251 perform NOR logic operations using protonation and complexsation with

Hg2+

and Zn2+

, respectively.216

Zong et al.217

used supramolecular interactions of compound 252 as the basis

for NAND gate. In the presence of ATP and H+ ions, intermolecular interactions of

252 become much stronger (π-π stacking + electrostatic interaction + hydrogen

bonding), which result in significant quenching of the fluorescence due to PET from

the adenosyl moiety. Margulies et al.218

reported first complex molecular arithmetic

system 253 based on fluorescent indicator fluorescein, integrating full adder and full

subtractor within the same molecular system. They have used acids and bases as input

248

249

250

251

56


signals, while changes in absorbance, transmittance, and fluorescence are used as

outputs. Protonation and deprotonation of fluorescein changes its absorption

spectrum. The neutral form of fluorescein shows only weak absorption at both

analytical wavelengths. In order to achieve full adder based on fluorescein, the

transmittance at 447 nm is assigned to the sum output, while absorbance at 474 nm as

carry output.

HN

HN

HN

O

NH2

OHO O

COOH

O O

OO

OO

O O

O

N

OO

O

O

OPrOPrOH HO

N

CH

OH

O2N

N

HC

HO

NO2

The calix[4]arene based fluorescent probe 254219

was activated by protons to

detect cesium in an acidic environment and potassium ions in an alkaline

environment. Furthermore, the fluorescence behaviour of 254 mimics the functions of

a logic gate. The fluorescent chemosensor 255 based on calixarene possessing imine

linkage can effectively recognize Cu2+

ions.220

The off–on–off fluorescent switching is

realized by the irradiation of compound 255 with ultraviolet and visible light. Based

on off–on–off switching, the corresponding INHIBIT (INH) logic gate was

constructed using ultraviolet and visible light.

Yuan et al.221

reported a fluorescent probe 256 possessing both BODIPY and

Rhodamine moieties in which chemical inputs of Hg2+

and Ba2+

ions have been used

to construct a combinational logic circuit using INHIBIT and YES logic operations at

the molecular level. Lee et al.222

reported a fluorogenic calix[4]arene-18-crown-6

derivative 257 whose fluorescence is quenched in the presence of Pb2+

ions, acid or

base. The combination of three inputs formulate logic functions such as NOR and

XNOR. The NOR logic gate operates at 395 nm in which the strong fluorescence

signal appears, only when neither of triethylamine nor Pb(ClO4)2 is added. Further,

XNOR gate operates only when both the inputs are added (triethylamine and HClO4)

252

253

254

255

57


or when neither of the two inputs is added. A new INHIBIT gate system was designed

using these combinational inputs (HClO4, Pb(ClO4)2 and triethylamine).

O OOH O

NHO

O O

OO

NB N

FF

ON

NN

O

O OO O

O O

OO NH

O

HN

OOO OHOH

N N

O O

OO OHOH

N N

OH

OH

ButHO

HO

But

Joseph et al. reported a calix[4]arene derivatives 258223

and 259224

bearing

four pyridyl moieties and hydroxymethyl salicylyl imine, respectively. An INHIBIT

(INH) logic gate has been generated by choosing Ag+ and Cys as input and by

monitoring the output signal at 445 nm that originates from the excimer emission of

258 in the presence of Ag+. On the other hand, compound 259 mimics the behaviour

of an INHIBIT logic gate in the presence of Zn2+

and HPO42-

ions.

Shiraishi et al.225

reported two output channel based on design 260 containing

two anthryl fluorophores linked with the diethylenetriamine chain. The interaction of

compound 260 with different transition metal in the presence of varying pH results in

formulation of various logic gates through dual channel emission. The fluorescent

sensor 261 responds to several heavy metals such as Zn2+

(In1), Cd2+

(In2), and Pb2+

(In3) with high intensity fluorescence (output).226

This strong fluorescence is observed

only in the absence of strong acids (In4). The integration of these four inputs results in

complex logic device containing one three-input OR, two input AND, and NOT gates.

Zhou et al.227

reported pyridine based chemosensor 262 possessing two pyrene

units. The application of three inputs of trifluoroacetic acid (In1), Zn2+

(In2), and

TETA (In3) results complex logic device through two output channels (excimer; out1)

and (monomer; out 2).

NH

HN

NH

N

O

ON

NNH2N

N

HN

HN

N

NN+ OH

N

Another simple molecular design 263 also acquires acid and base as inputs,

and the outputs are both in fluorescence channels at different wavelengths.228

The

luminescence of the BDPY central unit of compound 263 is controlled by two

260

261

262

263

256

257

258

259

58


processes: PET from the phenol moiety and ICT involving the dimethylaniline

moiety. Deprotonation of the phenol moiety results in complete quenching of the

fluorescence. However, protonation of the amino group results in a strong

hypsochromic shift (from 660 to 565 nm). Emission at 565 nm due to protonation of

amino group regarded as an output of the INH gate, while emission at 660 nm

corresponds to XNOR function. Application of positive logic to the INH output and

negative logic to the XNOR output results in binary half-subtractor.

Liu et al.229

reported molecular device 264 operated with acid and base inputs

and integrates three devices within one molecule: half-adder, half-subtractor, and

comparator. Furthermore, due to the presence of four spectrally different forms

(anion, neutral, cation dication) of compound 264, it is possible to implement binary

full adder and full subtractor within this molecule. This device is the only known

example of a molecular binary comparator. Andreasson et al.230

reported a molecule

device 265 which acts as both an AND and an XOR Boolean logic gate that share the

same two photonic inputs and comprises a half-adder, adding two binary digits with

only light as inputs and outputs. The AND function is based on the absorption

properties of the molecule, whereas the XOR function is based on an off-on-off

response of the fluorescence to the inputs that results from inter chromophore excited-

state quenching interactions.

NH

N N

N

NH

O

O

O

O

O

N

CNCN

N

CNNC

NO

NO2

N N

O

O-

O

O-

O

OO

OO

Magri et al.231

reported fluorescent chemosensor 266 which illustrate the AND

gate in response to the three electrolyte inputs Na+, H

+, and Zn

2+ in water with an

enhanced fluorescence signal. The compound 266 is a “lab-on-a-molecule” prototype

since a clinically relevant result would emerge from on-board information processing

of several sensory channels simultaneously in targeted cases.

The three-state molecular switch 267 based on spiropyran derivative was

synthesized by Raymo et al.232

The light and chemical stimulations induce the

switching of spiropyran derivative (SP) to the merocyanine forms ME and MEH.

264

265

266

59


This molecular system transduces the light and chemical inputs into optical outputs

through a complex sequence of logic operations. Further, Raymo et al.233

used SP,

ME and MEH forms of spiropyran derivative 267 to develop ultraminiaturized

processors which communicate intermolecular signals to a fluorescent probe at the

molecular level. The intermolecular communication is responsible for the transduction

of three input signals into a single optical output. The behaviour of these

communicating ensembles of molecules corresponds to that of a logic circuit

incorporating seven gates. The molecular switching of SP, ME and MEH forms of

spiropyran derivative 267 were further used to gate optical signals in response to

optical signals234

in which data are communicated optically but processed

electronically.

N+NO2

-O

MeMe

OH

N+NO2

HO

MeMe

OH

N

MeMe

OH

O

NO2

SP MEHME

N

O2SNH

SiEtO

OEt

OEt

The covalent immobilization of compound 268 on silicon nanowires (SiNWs)

was used to formulate the YES and INH logic operations with three chemical inputs

(pH, Hg2+

and Cl- or Br

- ions).

235 The SiNW-based fluorescent logic gate is

compatible with silicon-based semiconductor technology, thus providing a good

approach to build various logic gates to integrate more logic operations.

Applying the principles of molecular Boolean logic, Margulies et al.236

used a

molecular system 269 based on fluorescein conjugated with pyrene to develop a

reconfigurable molecular keypad lock that “opens” by inserting the right sequences of

three keys: EDTA (E), base (B), and UV light (U). Only keys E, B, and U hold the

correct inputs and can initiate a strong fluorescence at 525 nm that activates the green

channel, whereas keys E and U are enough for generating high emission at 390 nm

that triggers the blue channel. The other keys can hold a high concentration of

fluorescence quenchers, so if pressed, the password entry will fail. Suresh et al237

synthesized a chemosensor 270 which can detect Hg2+

in water and Hg2+

/ Cu2+

in

267

268

60


acetonitrile. The compound 270 was mimicked as a molecular keypad lock using

particular sequence of Cu2+

and F- as ionic inputs with strong fluorescence at 422 nm.

Another molecular device “molecular automaton” was developed by Ozlem et

al.238

The compound 271 works as a photodynamic therapy agent which release

singlet oxygen at a much larger rate when two cancer related cellular parameters (Na+

and H+) are above a threshold value within the same spatiotemporal coordinates. The

proposed logic gate would be actually an AND logic gate, the output would be singlet

oxygen. The molecular system 271 is an automaton which seek higher concentration

of both hydrogen and sodium ions for the release the cytotoxic agent (singlet oxygen).

O

O

HO

OH

NHNHN

NH

N NH

OO

OH

O

O

OH

O O

NO

NHOO

SO3H N

OOOO

NB

NI

CH3H3C

I

O

O

OO

O

F F

N N

N N N S

O

O

NNN

Li et al. 239

reported the fabrication a small organic molecule 272 based device

that has unexpected ternary memory device with I-V performance under a constant

reading voltage. This prototype device consumes less power and is easier to scale than

traditional devices. The molecule exhibits promising ternary behaviour under an

electric field, increasing the data-storage capacity of the device from 2n to 3n. This

device exhibits typical write once read-many-times (WORM) behaviour. The results

are promising for the development of an ideal ternary memory system and will open

the door to the development of next-generation HDDS devices.

Thus, from the above review of literature, it is clear that thiacalix[4]arene

scaffold is a unique host with vast possibilities of functionalization not only at the

wider and narrow rim but also at the bridging sulfide groups. The following

conclusion can be drawn from the above review of literature:

269 270

271

272

61


1. Thiacalix[4]arenes have better soft metal ion binding affinities compared to

calix[4]arenes due to the presence of sulfur atoms.

2. The incorporation of hard ligating sites like „O‟ make thiacalix[4]arenes

selective for hard metal ions.

3. The modifications at the sulfide groups make its chemistry interesting in

aqueous medium.

4. Thiacalix[4]arenes can be functionalized with different functional moieties

like amines, imines, crown ethers, amides, ureas/thioureas, etc. for binding of

different types of analytes (cations, anion and neutral molecules).

5. Compared to calix[4]arene, the chemistry of thiacalix[4]arenes with

appropriately appended chromogenic / fluorogenic groups is less explored for

sensing of cations and anions.

6. Thiacalix[4]arene scaffold is rarely employed for development of molecular

logic gates and molecular devices.

Thus, keeping in view of these observations, in the present investigation we

have designed and synthesized various thiacalix[4]arene derivatives possessing

amides, sulphonamides and (thio)ureas moieties. The results of our findings have been

discussed in following three chapters.

1. Chapter 2. Cation and anion recognition based on thiacalix[4]arene

2. Chapter 3. Bifunctional receptors based on thiacalix[4]arene

3. Chapter 4. Molecular switches and logic devices based on thiacalix[4]arene

62


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