supramolecular chemistry - ur · ∗ supramolecular chemistry-hosts: crown ethers, cryptands,...
TRANSCRIPT
02.06.04 lcns04 – ch02 1
∗ Concepts of Bonding- Through-bond and through space interaction- Photoelectron spectroscopy- Intermolecular interactions: Forces and Systems
∗ Supramolecular Chemistry- Hosts: Crown Ethers, Cryptands, Spherands, Calixarenes,
Siderophores, Cyclodextrines- Host-guest systems: Cation binding, anion binding, van der Waals
inclusion complexes- Hydrogen bonded systems- Artificial membranes
∗ Self-assembling- Electron donor-acceptor complexes - catenanes
∗ Natural Systems- DNA- Peptides, Proteins- Carbohydrates- Biological Membranes
Supramolecular Chemistry SUP/NAN/MR
02.06.04 lcns04 – ch02 2
» P. D. Beer, P. A. Gale, D. K. Smith, Supramolecular Chemistry, Vol. 74,Oxford University Press Inc., New York, 1999.
» J. W. Steed, J. L. Atwood, Supramolecular Chemistry, J. Wiley,Chichester, 2000.
» J. L. Atwood, J.-M. Lehn, J. E. D. Davies, D. D. MacNicol, F. Voegtle,Comprehensive Supramolecular Chemistry, Pergamon, Oxford, UK,1996.
» F. Vögtle, Supramolekulare Chemie, B.G. Teubner, Stuttgart, 1992.
References - Supramolecular Chemistry SUP/REV
02.06.04 lcns04 – ch02 3
Ø H.-H. Perkampus, Spektroskopie, VCH, Weinheim, 1993, S. 513
EOP/ANPhotoelectron spectroscopy
02.06.04 lcns04 – ch02 4
Intramolecular interaction through space
Ø .
QUA/EOP
Ionization potentials• Norbornene 8.97 eV• (Z)-2-Butene 9.12 eV• Norbornadiene:
8.7 eV and 9.55 eV
02.06.04 lcns04 – ch02 5
NAT/STR
The anomeric effect
02.06.04 lcns04 – ch02 6
Intermolecular interaction SUP
» P. Atkins The Elements of Physical Chemistry; Oxford University Press: Oxford,2001
» J. W. Steed, J. L. Atwood Supramolecular Chemistry; J. Wiley: Chichester,2000.
02.06.04 lcns04 – ch02 7
Ion-Ion interaction: Crystalline state SUP
02.06.04 lcns04 – ch02 8
Solid state structure of benzene: ππ ππ-stacking
SUP
» J. W. Steed, J. L. Atwood, Supramolecular Chemistry, J.Wiley, Chichester, 2000.
02.06.04 lcns04 – ch02 9
Helicates: Natural and synthetic systems SUP/CHI/MC
» Chem. Rev. 1997, 97, 2005.
Ø X-ray structures1: a double-stranded A-DNA2: trinuclear double-stranded helicate
02.06.04 lcns04 – ch02 10
Nonnatural helicates by self-assembling SUP/CHI/MC
» Chem. Rev. 1997, 97, 2005.
Ø Metallosupramolecularhelicates
Ø Ligands: 2,2‘-bispyridinesØ Cu(I) ions form
pseudotetrahedral complexes
02.06.04 lcns04 – ch02 11
Seminal work on supramolecular chemistry
SUP
Ø Crown ethers/corandsØ SpherandsØ Cryptands
O
OO
O
OO
NON
OO
O O
n
ROOR
OROR
RO
RO
dibenzo[18]crown-6 n = 2; [2.2.2]cryptand
spherand
"a cyclic hexa-meta-phenylene"
∗ Charles Pedersen∗ Donald Cram∗ Jean-Marie Lehn
02.06.04 lcns04 – ch02 12
Supramolecular chemistry: Articles SUP
Ø Crown ethers/corandsØ SpherandsØ Cryptands
∗ Charles Pedersen∗ Donald Cram∗ Jean-Marie Lehn
» Die Entdeckung der Kronenether (Nobel-Vortrag), C. J. Pedersen,Angew. Chem. 1988, 100, 1053-1059.
» Von molekularen Wirten und Gästen und ihren Komplexen (Nobel-Vortrag), D. J. Cram, Angew. Chem. 1988, 100, 1041-1052.
» Supramolekulare Chemie - Moleküle, Übermoleküle undmolekulare Funktionseinheiten (Nobel-Vortrag), J.-M. Lehn, Angew.Chem. 1988, 100, 91-116.
02.06.04 lcns04 – ch02 13
Host systems: Cation binding ligands SUP
Ø Coordination complexes of metal ionsØ MacrocylesØ Crown ethers/coronandsØ Lariat crown ethersØ Podands (acyclic hosts)Ø CryptandsØ SpherandsØ HelicatesØ CalixarenesØ Biological systems: Siderophores, Valinomycin
02.06.04 lcns04 – ch02 14
Crown ether complexes SUP
∗ Ionic diameters: Li+, 1.20 Å; Na+, 1.80 Å; K+, 2.66 Å
02.06.04 lcns04 – ch02 15
Formation of cryptates from cryptands andmetal ions (Mn+)
MR/SUP
[2.2.2.] cryptand cryptate a „metal complex“
02.06.04 lcns04 – ch02 16
Calixarenes: p-tert-Butylcalix[4]arene SUP/MR
02.06.04 lcns04 – ch02 17
Siderophores: Iron Sequestering
MR/SUP/BBM
enterobactin
complexation of Fe(III)
02.06.04 lcns04 – ch02 18
Molecular cavities: Cyclodextrines MR/SUP
O
O
O
HO
HO
O
O
O
O O
O
OOH
HO
O
O
OOO
O
O
O
O
OH
OH
O
O
O
OO
O
O
OHO
OH
O
O
OO O
H
H H
H
H
H
H
H
H
H
H
H
H
H
H H
O
OO
O
O
O
O
O
O
O
HO
HO
HOOH
OH
OH
OOO
O
O
O
O
O
OO
O
O
O
OH
HH
H
H
H
HH
HH
H
H
O
HO
O
O
O
OO
O
O
HO
HO
OH
OOO
O
O
O
O
OH
O
O
O HO
OO
O
O O
O
OHO
O
O
O
H
HH
HH
H
H
H
H
H
H
H
H
H
α-cyclodextrin β-cyclodextrin γ-cyclodextrin
apolar cavity polar rim
02.06.04 lcns04 – ch02 19
Binding constants (lg K) of crown ethers formetal ions
tms/SUP
[18]crown-6
• Na+, 4.32• K+, 6.10• Cs+, 4.62
[21]crown-7
• K+, 4.41• Cs+, 5.02
02.06.04 lcns04 – ch02 20
Log K values for cryptands of different size
MR/SUP
02.06.04 lcns04 – ch02 21
Calixarenes: Cationbinding
MR/SUP
02.06.04 lcns04 – ch02 22
Calixarenes: Cation/Anion binding
MR/SUP
02.06.04 lcns04 – ch02 23
Nitromethane inclusion complex with apyridinyl crown ether
tms/SUP
∗ Distances: C — H····N (2.21 Å); C—H····O (2.41 Å)
Ø E. Weber, S. Franken, H. Puff, J. Ahrendt, J. Chem. Soc.,Chem. Commun. 1986, 467.
02.06.04 lcns04 – ch02 24
Van der Waals inclusion complex (X-raystructure): p-tert-butylcalix[4]arene andtoluene
SUP
Ø G. D. Andreetti, R. Ungaro, A. Pochini, J. Chem. Soc.,Chem. Commun. 1979, 1005.
02.06.04 lcns04 – ch02 25
Problem: Sensing of Ammonium Ions
O
N
O
N
ON
oxazolin receptorfor ammonium ions
@ Fragen:∗ Wieso eignet sich der
Rezeptor 1 für dieBindung von Ammonium-Ionen?
∗ Welche Struktur hat derKomplex?
∗ Wie müssen Sie denRezeptor funktionalisieren,dass er chiraleAmmoniumsalzeunterscheiden kann?tripodal oxazoline receptor
» Organic Letters 2003, 5, 1419-1422.
02.06.04 lcns04 – ch02 26
Hydrogen bondingSUP/QUA
Ø J. W. Steed, J. L. Atwood, Supramolecular Chemistry, J. Wiley,Chichester, 2000.
02.06.04 lcns04 – ch02 27
Proton spongeSUP
Ø strong hydrogen bonds
N NMe
MeMeMe
H+
02.06.04 lcns04 – ch02 28
Crystal structure of oxalic acidSUP
02.06.04 lcns04 – ch02 29
Self-assembling via hydrogen bonding MR/SUP
NN
N OO
OHH
NN
N
N
NNHH
H HNN
N OO
OHH
self-assembling matrix
Cyanursäureamid
Isocyanursäure Isocyanursäure
N
NN
N
ZN
O
H
HN N
O
Z
N
H
H
H
N
NN
N
Z
NHH
N N
O
Z
Me
O
H
AT
GC
02.06.04 lcns04 – ch02 30
Rosettes MR/SUP
cyanuric acid + melamine insoluble complex
02.06.04 lcns04 – ch02 31
Problem: Flavin – receptor interaction MR/SUP
» G. Cooke, V. M. Rotello, Chem. Soc. Rev. 2002, 31, 275-286.
Ø Hydrogen bonding supported by ππ-stacking
02.06.04 lcns04 – ch02 32
Multiple hydrogen bonding MR/SUP
» J. Am. Chem. Soc. 2002, 124, 11064-11072.
N
N N
N
O
O
H
NH
R
NHH
A
D
D
D
A
A
02.06.04 lcns04 – ch02 33
Problem: Self assembling of theheterocyclic compound 1
MR/SUP
» J. Am. Chem. Soc. 2002, 124, 11064-11072.
02.06.04 lcns04 – ch02 34
Problem: Nanotubes by self assembling MR/SUP/NAN
» J. Am. Chem. Soc. 2002, 124, 11064-11072.
02.06.04 lcns04 – ch02 35
Structure of Phosphatidylcholin (L- α α-Lecithin)
NAT/BBM
02.06.04 lcns04 – ch02 36
Schematic representation of a phospholipidmembrane (5-6 nm in width) BBM/MMA
02.06.04 lcns04 – ch02 37
Surfactantstructuresin aqueoussolution
SUP/MMA/SAM
» E. Breitmaier, G. Jung, Organische Chemie:Grundlagen, Stoffklassen, Reaktionen, Konzepte,Molekülstruktur, 4th ed., Thieme, Stuttgart, 2001.
02.06.04 lcns04 – ch02 38
Synthesis of a [2]Catenane MR/SUP
» F. M. Raymo, J. F.Stoddard, in B. L.Feringa (Ed.):MolecularSwitches, Wiley-VCH, Weinheim2001, p. 219.
Ø Charge transferinteraction – self-assembling –template synthesis
02.06.04 lcns04 – ch02 39
Hydrogen bonded base pairing – DNANUC/SUP
NNN
N
Deoxyribose
NH
H
NN
O
O
Me
H
Deoxyribose
NNN
N
DeoxyriboseH
O
N HH
NN
N
O
H
Deoxyribose
HG = C
A = T
10.85 A
02.06.04 lcns04 – ch02 40
Thymine, adenine base pairing and thesecondary structure of DNA: Major andminor groove
NUC
∗ vdW: van der Waals interaction∗ a and d: acceptor and donor hydrogen bonding
Ø Science 1998, 282, 111-115.
02.06.04 lcns04 – ch02 41
NUC/ST
∗ A-T base pair (yellow); G-C base pair (blue)∗ identical positions of C1‘
Architecture of base-pair stacking
» L. Stryer, Biochemistry, W.H. Freeman, New York.
02.06.04 lcns04 – ch02 42
Structure andcomplementary basepairing in DNA
NUC/SUP
∗ Purine, pyrimidine bases,phosphoric acid, deoxyribose(ribose): Nucleoside,nucleotide, nucleic acid
02.06.04 lcns04 – ch02 43
NUC
∗ Watson-Crick –model
∗ The two strands arerunning in oppositedirection
Minorgroove
Majorgroove
Double stranded DNA molecule (B-form)
02.06.04 lcns04 – ch02 44
NUC
» The quest for the chemical roots of life, N. Hall, ChemicalCommunications (Cambridge, United Kingdom) 2004, 1247-1252.
Interesting article to read
02.06.04 lcns04 – ch02 45
A segment of a protein: right-handed helicalstructure (Myoglobin) BBM/SKE/NAT
02.06.04 lcns04 – ch02 46
Secondary structure of proteins: ß-pleatedsheet BBM/SKE/NAT
02.06.04 lcns04 – ch02 47
∗ Conformations of peptidic structures
Modulation of peptide nanostructures
Ø N. Voyer, in Topics in Current Chemistry, Vol. 184 (Ed.: F. P.Schmidtchen), Springer-Verlag, Berlin, 1996, pp. 1-37.
SKE/BBM
02.06.04 lcns04 – ch02 48
Polysaccharides: Amylose, Amylopectine,Cellulose NAT/CL/BBM
Amylopectine:high molecular weightaround one million glucose units
α-1,6‘-glycosidic bond
α-1,4‘-glycosidic bond
β-1,4‘-glycosidic bond
Amylose forms a left-handed helix
Cellulose has a one-dimensional structure with aslight helical turn, enforced byintramolecular hydrogen bonding
02.06.04 lcns04 – ch02 49
Representation of a biological membrane(„fluid mosaic model) BBM/BIO/MMA