novel network polymeric phthalocyanines: synthesis and characterization

Novel Network Polymeric Phthalocyanines:

Synthesis and Characterization

Ahmet Bilgin,*1 Cigdem Yagcı,1 Ufuk Yıldız2

1 Department of Science Education, Kocaeli University, 41300-Kocaeli, TurkeyE-mail: [email protected]

2 Department of Chemistry, Kocaeli University, Umuttepe Campus, 41380-Kocaeli, Turkey

Received: July 28, 2005; Revised: September 5, 2005; Accepted: September 6, 2005; DOI: 10.1002/macp.200500341

Keywords: electrical conductivity; heavy metal extraction; metal-free phthalocyanine; network polymeric phthalocyanine;tetranitrile

Summary: New p-xylylenebis-(oxa-thia-propan) bridgedmetal-free and metallophthalocyanine polymers were syn-thesized. The metal-free phthalocyanine polymer (3) wasprepared by the reaction of a tetranitrile monomer with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in pentanol. Ni- andCo-phthalocyanine polymers were prepared by reaction ofthe tetranitrile compound with the chlorides of Ni(II) andCo(II) in quinoline. Cu- and Zn-phthalocyanine polymerswere prepared by the reaction of the tetranitrile compoundwith the acetates of Cu(II) and Zn(II) and DBU in amylalcohol. Yellow PbO and Fe(CO)5 were used to prepare Pb-and Fe-analog polymers, respectively. The Co-phthalocyaninepolymer was also prepared using ethylene glycol instead ofquinoline in the presence of the catalyst ammonium moly-

bdate. (3) was chemically doped with iodine. The electricalconductivities of the polymeric phthalocyanines measured asgold sandwiches were found to be 10�9–10�7 S � cm�1 in avacuum and in argon. The electrical conductivity of iodinedoped metal-free phthalocyanine (3a) was found to beapproximately 57 times higher than that of the undopedversion. The extraction ability of (3) was also evaluated inTHF using transition metal picrates, such as Ag1þ, Hg2þ,Pb2þ, Cd2þ, Cu2þ and Zn2þ. The extraction affinity of (3) forAg1þ was found to be highest in the heterogeneous phaseextraction experiments. All the novel compounds were char-acterized using elemental analysis, UV-Vis, FT-IR, NMR andMS spectral data and DSC.

Synthesis of new network polymeric phthalocyanines.

Macromol. Chem. Phys. 2005, 206, 2257–2268 � 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper DOI: 10.1002/macp.200500341 2257

Introduction

Phthalocyanines (Pcs), one of the best known synthetic

porphyrin analogues, are highly versatile and stable

chromophores with unique physicochemical properties that

make them, alone or in combination with many other

electro- and photoactive moieties, ideal building blocks for

the construction of molecular materials with special elec-

tronic and optical properties.[1] Pcs have macrocyclic 18pelectron systems that are known to be the source of

semiconductor characteristics, and they are characterized

by high thermal and reasonable chemical stability.[2] Pcs

show interesting photophysical properties and both photo

and dark semiconductivity, which makes them particularly

interesting for use in more advanced technological ap-

plications, such as optical recording, non-linear optics, light

emitting diodes, a basis for optical sensing, photodynamic

therapy and gas sensors.[3]

Compared to low molecular weight phthalocyanines,

relatively few reports describe the synthesis and proper-

ties of polymeric phthalocyanines. For the polycyclo-

tetramerization, bifunctional monomers based on

tetracarbonitriles for polymers,[4–9] various oxy-, arylene-

dioxy- and alkylenedioxy-bridged diphthalonitriles

for polymers[10–14] and other nitriles[15–17] or tetracarbox-

ylic acid derivates[18–21] have been employed, mainly in

the presence of metal salts or metals. The polymers

exhibit not only very large and accessible surface areas[22]

but also good thermal stabilities under inert gas up to

�500 8C and under oxidative conditions up to �350 8C.

The conductivities of the semiconducting polymeric

phthalocyanines are higher than those of the corresponding

low molecular weight phthalocyanines.[23–28] However,

polymeric phthalocyanines can only be utilized in some

fields because of their insolubility in water and common

solvents.[29]

Recently, we have reported phthalocyanines containing

spherical or cylindrical macrotricyclic, macrobicyclic,

diloop macrocyclic and 12-membered diazadioxamacro-

cycle moieties.[30–35]

A flexible p-xylylenebis-(oxa-thia-propan) bridged tet-

ranitrile monomer compound can be more advantageous

than a rigid bis(phthalonitrile) such as 1,2,4,5-tetracyano-

benzene in the polycyclotetramerization reaction for the

synthesis of polymeric phthalocyanines. Also, the presence

of such flexible units increases the electrical conductivity of

polymeric phthalocyanines due to a cofacially stacked

arrangement of phthalocyanine units.

In this paper, we describe the synthesis and character-

ization of metal-free and metallophthalocyanine polymers

containing p-xylylenebis-(oxa-thia-propan) moieties. We

examined the electrical conductivities of the polymers as

gold sandwiches. The viscosities of all the polymers and the

heavy metal extraction ability of polymer (3) were also

examined.

Experimental Part

Materials

Potassium hydroxide (KOH), phosphorus pentoxide (P2O5),1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), ethyl alcohol,pentanol, dimethyl sulfoxide (DMSO), dimethylformamide(DMF), tetrahydrofuran (THF), chloroform, petroleum ether,benzene, quinoline and sulfuric acid were obtained fromMerck and used as received. Potassium carbonate (K2CO3) wasreceived from Merck and used after drying in an oven at 250 8Cfor 36 h. 2-Mercaptoethanol and a, a0-dibromo-p-xylene werereceived from Fluka and used as received. All organic sol-vents were dried and purified as described by Perrin andArmarego.[36] 4-Nitrophthalonitrile was synthesized asdescribed in the literature.[37]

Preparation of p-Xylylene-bis-(1-hydroxy-3-thia-propan) (1)

A mixture of finely powdered KOH (1.34 g, 20 mmol) andabsolute ethanol (45 mL) was put into a 300 mL three neckedflask fitted with a condenser, a magnetic stirrer and a droppingfunnel, and dissolved under a nitrogen atmosphere. 1.56 g(20 mmol) of 2-mercaptoethanol was slowly added to thesolution after 1 h of stirring. 2.7 g (10 mmol) of a,a-dibromo-p-xylene were dissolved in 25 mL of absolute ethanol by slightheating and then added dropwise to the solution at 90 8C over aperiod of 3 h. After this, the reaction mixture was stirred andheated under reflux for a further 12 h. Aliquots were takenperiodically to check the completeness of the reaction usingthin layer chromatography (TLC) [7:3 chloroform: petroleumether] until the reaction had ended. A quarter of the solvent wasevaporated and the solution was then cooled to room tem-perature and filtered to remove the precipitating salt. Thefiltrate was distilled under a vacuum and cooled to give a crudeproduct. The crude product was filtered and washed withdistilled water and petroleum ether, respectively. The productwas dried under a vacuum over P2O5 and recrystallized fromthe minimum amount of methanol. The yield was 92%. Thefinal white solid (1) (m.p. 65–67 8C) was soluble in commonorganic solvents such as chloroform, dichloromethane, benz-ene, DMF and DMSO.

1H NMR (CDCl3): d¼ 7.26 (s, 4H, Ph), 3.70 (s, 4H, S–CH2–Ph), 3.66–3.59 (q, 4H, S–CH2–CH2OH), 2.64–2.59 (t, 4H, S–CH2–CH2OH), 2.11–2.06 (t, 2H, –OH).

13C NMR (CDCl3): d¼ 137.50 (CAr–CH2S–), 129.27(CHAr), 61.21 (S–CH2–CH2OH ), 36.01 (S–CH2–CH2OH),34.11 (CAr–CH2S).

FT-IR (KBr): 3 324 (OH), 3 057 (ArH), 2 954–2 827 (CH2),1 508, 1 475, 1 350, 1 238, 1 089–1 045 (OCH2), 856, 705,607 cm�1.

(C12H18S2O2) (258.40): Calcd. C 55.78, H 7.02, S 24.82;Found C 55.65, H 6.83, S 25.03.

MS (EI): m/z (%)¼ 356.43(33.75) [Mþ2KþH2Oþ2]þ,297.09 (36.25) [MþK]þ, 281.08 (100) [MþNa]þ, 259.04(13.75) [Mþ1]þ, 257.04 (16.87) [M�1]þ, 181.00 (33.70) [M–(S(CH2)2OH)]þ, 134.91 (43.75) [M–(S(CH2)2OHþ(CH2)2OHþ1)]þ, 104.90 (20.62) [M�2(S(CH2)2OH)]þ.

2258 A. Bilgin, C. Yagcı, U. Yıldız

Macromol. Chem. Phys. 2005, 206, 2257–2268 www.mcp-journal.de � 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Preparation of Tetranitrile Monomer (2)

To a 100 mL round bottom flask, equipped with a magneticstirrer, condenser and a CaCl2 drying tube, were added4-nitrophthalonitrile (2.67 g, 15.25 mmol) and dry DMF(10 mL) at 50 8C which dissolved under a nitrogen atmosphere.1.97 g (7.62 mmol) of (1) was added to the solution. 3.15 g(22.86 mmol) of freshly ground anhydrous K2CO3 were addedto the solution in eight equal portions at 2 h intervals withefficient stirring and the reaction system was stirred at the sametemperature (50 8C) for 5 d. Aliquots were taken periodically tocheck the completeness of the reaction using thin layerchromatography (TLC) [7:2:1 chloroform:petroleum ether:-methanol] until the reaction ended. After cooling, the reactionmixture was poured into 100 mL of a cold HCl (5 wt.-%)solution to yield a crude product. This precipitate was stirredat room temperature for 24 h. At the end of this time, theprecipitate was isolated by filtration and was first washed withdistilled water, until the filtrate was neutral, and then diethylether before drying in vacuo over P2O5. Recrystallization froma mixture of ethanol: chloroform (3:1; v/v) gave a light greenproduct. The yield was 3.6 g (82%). The product had a meltingpoint of 178–179 8C. The final light green solid (2) was solublein CHCl3, DMF, DMSO, pyridine and dichloromethane.

1H NMR (CDCl3): d¼ 7.91–7.87 (d, 2H, ArH), 7.71–7.67(d, 2H, ArH), 7.46–7.37 (dd, 2H, ArH), 7.25 (s, 4H, Ph), 3.75(s, 4H, S–CH2–Ph), 4.11–4.03 (t, 4H, S–CH2–CH2O–Ar),2.87–2.82 (t, 4H, S–CH2–CH2O–).

13C NMR (DMSO-d6): d¼ 162.11 (C4), 137.50 (C12),136.02 (C6), 129.56 (C13), 120.68 (C5), 120.32 (C3), 117.15(C2), 116.48–116.04 (C8, C7), 107.01(C1), 68.97 (C9 ), 35.97(C10), 29.84 (C11).

FT-IR (KBr): 3 065 (aromatic CH), 2 945–2 856 (CH2),2 224 (C N), 1 598 (aromatic–C C–), 1 564, 1 504, 1 417,1 320, 1 290 (Ar–O–C), 1 094, 850, 713, 527 cm�1.

(C28H22S2N4O2) (510.64): Calcd. C 65.86, H 4.34, N 10.97,S 12.56; Found C 66.13, H 4.70, N 10.53, S 12.78.

MS(EI): m/z (%)¼ 510.01 (25.02) [M]þ, 403.43 (15.30),358.40 (51.88), 356.33 (100), 330.30 (71.87), 304.21 (65.01),256.10 (38.13), 118.92 (43.75), 106.06 (47.50).

Preparation of Metal-Free Polymeric Phthalocyanine (3)

A standard Schlenk tube was charged with 0.510 g (1 mmol) ofcompound (2), 5 mL of dry pentanol and 0.155 g (0.15 mL,1 mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) undera nitrogen atmosphere and degassed several times. Thetemperature was gradually increased up to 90 8C and the flaskwas degassed again with nitrogen. Then the reaction mixturewas stirred at 145 8C for 5 h. After the reaction mixture wascooled and decanted, the remaining dark green solid wasstirred with 25 mL of a methanol:petroleum ether mixture (1/1;v/v). The dark green product (3) was filtered off, washed withhot methanol and diethyl ether and then dried in vacuo at100 8C. The yield was 0.6 g (72%). The product had a meltingpoint of 185 8C. The final petroleum greenish solid was solublein H2SO4, hot pyridine, hot DMSO, acetic acid and was poorlysoluble in chloroform, dichloromethane and THF.

FT-IR (KBr): 3 270 (N–H), 3 060 (aromatic CH), 2 990–2 840 (CH2), 2 222 (C N), 1 624, 1 595 (aromatic –C C–),

1 564, 1 502, 1 420, 1 325, 1 260 (Ar–O–C), 1 240, 1 040, 990,870, 720, 540 cm�1.

(C112H90S8N16O8)n (2 044.58)n: Calcd. C 65.80, H 4.44,N 10.96, S 12.55; Found C 66.21, H 5.96, N 10.74, S 13.12 [forCN end groups].

Synthesis of Ni-Containing Polymer (4)

A standard Schlenk tube was charged with 0.510 g (1 mmol) oftetranitrile compound (2), 2.5 mL of dry quinoline and 0.122 g(0.5 mmol) of NiCl2 � 6H2O and degassed three times withnitrogen. The temperature was increased up to 190–200 8C andthe contents treated for 5 h under reflux and a nitrogen inertatmosphere. The colour of the mixture became green after45 min. The reaction mixture was stirred for 12 h. 50 mL of amethanol:water (1:1; v/v) mixture was added to the system andstirred at room temperature for 30 min. The dark green productwas filtered off and washed with hot methanol, DMF, distilledwater and diethyl ether, respectively. The final product (4) wasdried over P2O5 at 100 8C. The yield was 0.66 g (65%).

FT-IR (KBr): 3 410 (imide N–H), 3 050 (aromatic CH),2 940–2 830 (CH2), 1 770 (sym. C O), 1 710 (asym. C O),1 604 (aromatic –C C–), 1 574, 1 499, 1 415, 1 320, 1 230 (Ar–O–C), 1 110–1 020, 720 cm�1.

(C112H92S8N12O16Ni)n (2 177.27)n: Calcd. C 61.79, H 4.26,N 7.72, S 11.78, Ni 2.70; Found C 62.16, H 4.93, N 7.48,S 12.36, Ni 2.84 [for imide end groups].

Synthesis of Co-Containing Polymer (Route 1) (5)

A round bottom flask was charged with 0.510 g (1 mmol) oftetranitrile compound (2), 3 mL of dry quinoline and 0.121 g(0.5 mmol) of CoCl2 � 6H2O and degassed three times withnitrogen. The reaction was heated at 220 8C for 8 h under refluxand a nitrogen inert atmosphere. The reaction mixture wascooled and then 50 mL of ethyl alcohol was added. Thereaction was filtered after 3 h of stirring. The solid part waswashed with hot methanol, hot ethanol, distilled water anddiethyl ether, respectively. The final product (5) was dried overP2O5 at 100 8C. The yield was 0.68 g (69%).


(C112H92S8N12O16Co)n (2 177.50)n: Calcd. C 61.78, H 4.26,N 7.72, S 11.78, Co 2.71; Found C 62.06, H 4.52, N 7.89, S12.21, Co 2.92.

Synthesis of Co-Containing Polymer (Route 2) (5)

A round bottom flask was charged with 0.510g (1 mmol) oftetranitrile compound (2), 2.5 mL of ethylene glycol, 40 mg ofammonium molybdate and 0.121 g (0.5 mmol) of CoCl2 �6H2O and degassed several times with nitrogen. The reactionwas heated at 210–220 8C for 6 h under reflux and a nitrogeninert atmosphere. The reaction mixture was cooled and then50 mL of ethyl alcohol added. The reaction was filtered after 1 hof stirring. The solid part was washed with hot methanol, hotethanol, DMF, distilled water and diethyl ether, respectively.

Novel Network Polymeric Phthalocyanines: Synthesis and Characterization 2259


The final product (5) was dried over P2O5 at 100 8C. The yieldwas 0.76 g (76%).

The spectral analysis of (5) was the same to that of the Co-containing polymer synthesized via route 1.

Synthesis of Fe-Containing Polymer (6)

A mixture of tetranitrile compound (2) (0.510 g, 1 mmol) andethylene glycol (20 mL) was kept in a round bottom flask. Thetemperature was quickly increased up to 210 8C and refluxedunder a nitrogen atmosphere. 0.075 mL (0.10 g, 0.5 mmol) ofFe(CO)5 was slowly added with a syringe and left stirring at210 8C. After 7 h of stirring, the reaction mixture was cooled toroom temperature and precipitated with 100 mL of ethylalcohol. The amorphous green product was filtered off andwashed with 100 mL (10 vol.-%; v/v) of HCl to remove excessiron and then with distilled water until the residue washingwater was neutral. The final product was dried over P2O5 at100 8C. The yield was 0.59 g (64%).

FT-IR (KBr): 3 417 (imide N–H), 3 058 (aromatic CH),2 960–2 829 (CH2), 1 773 (sym. C O), 1 730 (asym. C O),1 605 (aromatic –C C–), 1 564, 1 485, 1 410, 1 328, 1 270,1 240 (Ar–O–C), 1 100–1 020, 760 cm�1.

(C112H92S8N12O16Fe)n (2 174.41)n: Calcd. C 61.87, H 4.26,N 7.73, S 11.80, Fe 2.57; Found C 61.26, H 4.74, N 7.56,S 12.32, Fe 2.73.

Synthesis of Pb-Containing Polymer (7)

A mixture of tetranitrile compound (2) (0.510 g, 1 mmol),yellow lead (II) oxide (PbO) (0.112 g, 0.5 mmol) and ethyleneglycol (10 mL) were charged in a round bottom flask anddegassed three times under a nitrogen atmosphere. The reac-tion was heated at 190 8C for 8 h under reflux and a nitrogeninert atmosphere. After cooling, 5 mL of HCl (10 vol.-%; v/v)was added to the system and stirred for 30 min. The dark greencrude product was filtered and washed with ethanol and HCl(5 vol.-%; v/v) to remove an excess of PbO. The product waswashed with distilled water until the residue washing water wasneutral. The product was then washed with diethyl ether andput in a desiccator. The final product was dried under a vacuumover P2O5 at 100 8C. The yield was 0.54 g (56%).

FT-IR (KBr): 3 380 (imide N–H), 3 056 (aromatic CH),2 982–2 830 (CH2), 1 775 (sym. C O), 1 712 (asym. C O),1 604 (aromatic –C C–), 1 554, 1 492, 1 412, 1 320, 1 262,1 230 (Ar–O–C), 1 105–1 026, 840, 735 cm�1.

(C112H92S8N12O16Pb)n (2 325.75)n: Calcd. C 57.84, H 3.99,N 7.23, S 11.03, Pb 8.91; Found C 58.23, H 4.33, N 6.86,S 11.58, Pb 8.57.

Synthesis of Cu-Containing Polymer (8)

A round bottom flask was charged with 0.510 g (1 mmol) oftetranitrile compound (2), 0.102 g (0.5 mmol) of Cu(CH3

COO)2 �H2O and 5 mL of amyl alcohol. The temperature wasincreased up to 160 8C and degassed three times under anitrogen atmosphere. Then, 0.15 mL (0.155 g, 1.0 mmol) ofDBU was added drop by drop with a syringe into the system.The reaction was heated at 160 8C for 8 h under reflux and a

nitrogen atmosphere. The reaction mixture was cooled, 5 mLof pentanol added and then stirred for 45 min. The crudeproduct was filtered and washed with hot ethanol, distilledwater and diethyl ether. The final product was dried under avacuum over P2O5 at 100 8C. The yield was 0.96 g (79%).

FT-IR (KBr): 3 350 (imide N–H), 3 057 (aromatic CH),2 924–2 855 (CH2), 1 770 (sym. C O), 1 702 (asym. C O),1 600 (aromatic –C C–), 1 485, 1 434, 1 328, 1 282, 1 226 (Ar–O–C), 1 188–1 012, 950, 737 cm�1.

(C112H92S8N12O16Cu)n (2 182.11)n: Calcd. C 61.65, H 4.25,N 7.70, S 11.76, Cu 2.91; Found C 61.24, H 4.69, N 8.13,S 11.43, Cu 3.36.

Synthesis of Zn-Containing Polymer (9)

A round bottom flask was charged with 0.510 g (1 mmol) oftetranitrile compound (2), 0.115 g (0.5 mmol) of zinc acetatedihydrate [Zn(CH3COO)2 � 2H2O] and 10 mL of amyl alcoholand the temperature was increased up to 160 8C. 0.15 mL(0.155 g, 1.0 mmol) of DBU was added drop by drop with asyringe to the system at the same temperature. The reaction washeated at 160 8C for 12 h under reflux and a nitrogenatmosphere. After cooling, 50 mL of a methanol-water mixture(1:1; v/v) was added to the system and stirred for 1 h. The greencrystals produced were filtered and washed with hot DMF,methanol, distilled water and petroleum ether, respectively.The final product was dried under a vacuum over P2O5 at100 8C. The yield was 0.88 g (60%).


(C112H92S8N12O16Zn)n (2 183.93)n: Calcd. C 61.60, H 4.25,N 7.70, S 11.75, Zn 2.99; Found C 61.95, H 5.03, N 7.41,S 11.84, Zn 2.58.

Iodine Doping. Reaction of Polymeric Metal-FreePhthalocyanine with Iodine (3a)

A mixture of metal-free polymeric phthalocyanine (3)(100 mg), iodine (I2) (100 mg) and heptane (25 mL) werecharged in a flask and stirred at 45 8C for 48 h under a nitrogenatmosphere. At the end of the reaction time, the colour of themixture became dark green. After cooling, the mixture wasfiltered and washed with diethyl ether. The final dark greensolid product was dried in a desiccator under a vacuum overP2O5 for 12 h (10�3 torr). The yield was 0.13 g (65%).

The Conversion of the Cyano End Groups of the Metal-FreePolymeric Phthalocyanine into Imido Groups (3b)

A sample of the metal-free phthalocyanine (3) (150 mg) wasdissolved in H2SO4 (96 wt.-%) at room temperature using thesmallest amount of H2SO4 possible. After 3 h of stirring, thereaction mixture was filtered. The filtered part was poured intoan excess amount of an ice-water mixture. The dark greencrude product was washed with distilled water until the residuewashing water was neutral. Then the final product was washedwith ethanol and diethyl ether and dried under a vacuum overP2O5 at 110 8C. The yield was 0.12 g (80%).



FT-IR (KBr): 3 385 (imide N–H), 3 290 (N–H), 3 055(aromatic CH), 2 980–2 825 (CH2), 1 772 (sym. C O),1 710 (asym. C O), 1 600, 1 542, 1 498, 1 322, 1 280 (Ar–O–C), 1 230, 1 195, 1 030, 865, 732, 542 cm�1.

(C112H94S8N12O16)n (2 120.58)n: Calcd. C 63.44, H 4.47,N 7.93, S 12.07; Found C 63.69, H 4.63, N 7.32, S 12.53.

Measurement of the Heavy Metal-Binding Properties of thePolymeric Metal-Free Phthalocyanine (3)

The extraction properties of (3) were investigated under solid-liquid phase conditions using heavy metal picrates (Ag1þ,Cd2þ, Cu2þ, Hg2þ, Pb2þ and Zn2þ) as substrates and meas-uring with UV-Vis the amounts of picrate in the THF phasebefore and after treatment with polymers in suspension.Suspensions were prepared by mixing 25 mg of the polymericmetal-free phthalocyanine (3), which was ground in a ballmillfor 3 h to assure the same particle size, and the heavy metalpicrate solutions (picrate solutions were prepared in 25 mL ofTHF by reacting equivalent amounts of each heavy metalnitrate and picric acid) in 25 mL of 10�3 M THF. The preparedsuspensions were put in plastic bottles and shaken vigorouslyfor 24 h at room temperature. Results and experimentalconditions are reported in Table 1. In the absence of the host(3), a blank experiment, no metal ion picrate extraction wasdetected. The extractability was determined based on theabsorbance of the picrate ion in the THF suspensions. Theextractability was calculated using Equation (1):

Eð%Þ ¼ ½ðA0 � AÞ=A0� � 100 ð1Þ

where A0 is the absorbance in the absence of a ligand. A denotesthe absorbance in the THF suspension phase after extraction.

Characterization

1H NMR spectra were recorded on a Varian Mercury Plus300 MHz spectrometer with CDCl3 and DMSO-d6 as solventsand tetramethylsilane as the internal standard.

13C NMR spectra were recorded on a Varian Mercury Plus75 MHz spectrometer with DMSO-d6 as the solvent andtetramethylsilane as the internal standard.

Transmission IR spectra of samples were recorded on a FT-IR spectrophotometer (Schimadzu FTIR-8201 PC) in thespectral range 4 000–400 cm�1. Pellets consisting of about

100 mg of KBr powder containing the finely ground powder ofeach sample were made less than 1 h before recording.

UV-Vis spectra were recorded on a model Schimadzu1601 UV-Vis spectrometer using a 1 cm pathlength quartz UVcell.

The d.c. conductivity was measured using an Autolab 30Voltammetry-FRA 2 frequency analyzer. The frequency rangewas 100 Hz–1 MHz and the applied amplitude (rms) was10 mV.

Mass spectra were measured on a Varian MAT 711spectrometer and on a Micromass Quatro LC/ULTIMA LC-MS MS spectrometer.

The elemental analysis of the compounds was conducted ona CHNS-932 LECO instrument.

The metal contents of the metallophthalocyanines weredetermined using a Unicam 929 AA spectrophotometer.

Differential scanning calorimetry (DSC) was performedon a Setaram DSC 141 under a nitrogen atmosphere with aheating rate of 10 8C �min�1 over the temperature range 50–700 8C.

The intrinsic viscosities of freshly prepared dilute solutionsof phthalocyanine polymers were measured in concentratedH2SO4 at 25 8C using an Ubbelohde viscometer.

The melting points of the compounds were determined usingan electrothermal melting point apparatus. All melting pointsare uncorrected.

Results and Discussion

Metal-free and metallophthalocyanine polymers were

synthesized in three steps (Scheme 1). In the first step,

p-xylylenebis-(1-hydroxy-3-thia-propan) (1) was synthe-

sized by the reaction of a,a-dibromo-p-xylylene with

2-mercaptoethanol in ethanol using KOH as the base. In

the second step, the base-catalyzed nucleophilic aromatic

nitro displacement[38,39] of 4-nitrophthalonitrile with (1)

afforded the tetranitrile monomer (2). In the last step, metal-

free and metallophthalocyanine polymers were synthe-

sized. The metal-free phthalocyanine polymer (3) was

synthesized by the polycyclotetramerization reaction of (2)

with a basic catalyst, DBU, in pentanol. Ni-containing

phthalocyanine polymer (4) was synthesized by the reaction

of (2) with NiCl2 � 6H2O in a high boiling solvent,

quinoline. Co-containing phthalocyanine polymer (5) was

synthesized by two different methods. In the first route, (5)

was synthesized by the reaction of (2) with CoCl2 � 6H2O in

quinoline. In the second route, (5) was synthesized by

the reaction of (2) with CoCl2 � 6H2O and ammonium

molybdate as a catalyst in ethylene glycol. We could not

synthesize the Co-containing phthalocyanine polymer via

the second route without using ammonium molybdate.

In the second route, the yield was relatively higher than that

of the first route, probably due to the presence of ammonium

molybdate as a catalyst. Fe-containing phthalocyanine

polymer (6) was synthesized by the reaction of (2) with

Fe(CO)5 in ethylene glycol. Pb-containing phthalocyanine

polymer (7) was synthesized by the reaction of (2) with

Table 1. Heavy metal picrate extractions for (3) under solid/liquid two-phase conditions.

Metal ion Extractability ofmetal-free polymericphthalocyanine (3)

lmax of metalpicrate

% nm

Ag1þ 65.37 358Hg2þ 40.57 352Pb2þ 27.20 355Cd2þ 34.11 345Cu2þ 48.17 360Zn2þ 6.85 350



yellow lead (II) oxide (PbO) in ethylene glycol. Cu-con-

taining phthalocyanine polymer (8) was synthesized by the

reaction of (2) with Cu(CH3COO)2 �H2O in amyl alcohol.

Zn-containing phthalocyanine polymer (9) was synthesized

by the reaction of (2) with zinc acetate dihydrate in amyl

alcohol. Iodine doped metal-free phthalocyanine polymer

(3a) was prepared by the reaction of metal-free polymeric

phthalocyanine (3) and iodine in heptane. In order to

compare the polymerization degrees of all polymers, the

cyano end groups of the metal-free phthalocyanine polymer

were converted into imido end groups (3b).

The molecular weights of the polymers could not be

determined using traditional methods because of their poor

solubility in organic solvents, but also by comparison of the

IR absorption bands of the end groups with those of the

bridging groups.[10,40,41]

The disappearance of C–Br (620 cm�1) and the presence

of the O–H stretching vibration which occurs as a strong,

broad absorption at 3 324 cm�1 in the IR spectrum of (1)

confirmed the formation of (1). Elemental analysis and EI

mass spectral data were satisfactory: 259 [Mþ1]. The 1H

NMR spectrum of (1) showed new signals at d¼ 3.66–3.59

Scheme 1. Synthesis of new network polymeric phthalocyanines.



(q, 4H, S–CH2–CH2OH), 2.64–2.59 (t, 4H, S–CH2–

CH2OH) and 2.11–2.06 (t, 2H, –OH). The proton-

decoupled 13C NMR spectrum of (1) clearly indicated the

presence of primer alcohol carbon atoms and SCH2 carbon

atoms at d¼ 61.21 (S–CH2–CH2OH ) and 36.01 (S–CH2

–CH2OH), respectively.

In the IR spectrum of (2), the disappearance of the NO2

and OH stretches, along with the appearance of new bands

at 2 224 cm�1 and 1 290 cm�1 arising from C N and Ar–O

–C groups, respectively, are in agreement with the proposed

structure. Elemental analysis and EI mass spectral data

were satisfactory: 510[M]þ. The 1H NMR (CDCl3)

spectrum of (2) showed new signals at d¼ 7.91–7.87

(d, 2H, ArH), 7.71–7.67 (d, 2H, ArH), 7.46–7.37 (dd, 2H,

ArH), 3.75 (s, 4H, S–CH2–Ph), 4.11–4.03 (t, 4H, S–CH2–

CH2O–Ar) and 2.87–2.82 (t, 4H, S–CH2–CH2O–). The

resonances absorbed at d¼ 162.11 (C4), 137.50 (C12),

136.02 (C6), 129.56 (C13), 120.68 (C5), 120.32 (C3), 117.15

(C2), 116.48–116.04 (C8, C7), 107.01(C1), 68.97 (C9),

35.97 (C10), 29.84 (C11) in the 13C NMR (DMSO-d6)

spectrum of compound (2) should be related to correspond-

ing carbon atoms.

As can be seen in Figure 1, the IR spectrum of the metal-

free phthalocyanine polymer (3) was slightly broadened

and reduced in intensity, which can be attributed to a

difficulty in grinding the sample to a small particle size.

Characteristic peaks for phthalocyanines were observed.

The peaks at 3 270 and 1 040 cm�1 are the characteristic

metal-free phthalocyanine N–H stretching and pyrrole ring

vibration bands. Besides, deuterium exchange with D2O

causes N–H absorption in the infrared to shift from 3 270 to

2 478 cm�1, confirming the IR assignment. Aweak –C N–

absorption at 1 624 cm�1 was detected. Also, 1 240 cm�1

(Ar–O–C) and 650 cm�1 bands were present in the spec-

trum. Elemental analysis was satisfactory.

The IR spectra of the metallophthalocyanine polymers

(4–9) were very similar, with the exception of the metal-

free phthalocyanine polymer (3) which showed an N–H

stretching band at 3 270 and 1 040 cm�1 due to the inner

core.[42,43] These bands are especially beneficial for the

characterization of metal-free phthalocyanine polymers, as

there is little frequency dependence on ring substitution and

they are not overlapped by strong tetranitrile monomer

absorptions.[5] These bands disappeared in the spectra of the

metallophthalocyanine polymers. Metal–N vibrations

were expected to appear at 400–100 cm�1, but they were

not detected in KBr pellets.[42,43]

Some clear differences were observed in the IR spectra of

the metallophthalocyanine polymers (4–9) when compared

to that of the metal-free phthalocyanine polymer (3). In

the IR spectra of the complexes, the end groups of the metal-

free phthalocyanine polymer were cyano groups

(2 220 cm�1) while the end groups of the metallophthalo-

cyanine polymers were imido groups (1 770–1 710 cm�1).

The existence of imido groups in the case of metal-

lophthalocyanine polymers was attributed to the presence

Figure 1. FT-IR spectra of (2), (3) and (3a).



of moisture during work-up. There is little shift to longer

wavelength numbers for most of the IR bands of the metal

complexes with respect to the metal-free analogues.[5,44]

The IR spectrum for the iodine doped metal-free phth-

alocyanine polymer (3a) showed characteristic phthalo-

cyanine absorptions.[45–47] As iodine doping increased, the

IR peaks broadened and were finally obscured due to the

superposition of electronic excitation absorption.[48,49] As

can be seen in Figure 1, the IR spectrum of iodine doped

polymer was very broadened.

In the IR spectrum for (3b), the disappearance of the peak

at 2 220 cm�1 due to the cyano groups of (3) and the

appearance of new peaks at �1 770–1 710 cm�1 due to the

imido groups supported the conversion of the cyano groups

into imido groups. Owing to the insolubility of the poly-

meric phthalocyanines in organic solvents and different

annelations of the phthalocyanine units, polymer molecular

weights are difficult to determine. One possible procedure

for determining the degree of polymerization is IR spec-

troscopy, by comparison of the intensity of the end cyano

groups to other ring vibrations. Although this method has

been applied in only few cases,[23] we used it after con-

verting the cyano end groups of the metal-free phthalocya-

nine polymer into imido end groups. After this, the ratios of

the absorption intensities of the Ar–O–C groups of the

polymers (1 240 cm�1) to the asymmetric C O groups of

the imides (�1 715 cm�1) were calculated [compound/

log10 I1 240/I1 715: (3b)/0.81, (4)/4.50, (5)/1.30, (6)/1.36, (7)/

0.83, (8)/0.86, (9)/3.85]. The polymerization degrees

follow the order: (4)> (9)> (6)> (5)> (8)> (7)> (3b).

The lower solubility of the phthalocyanine polymers

meant that their spectra could be obtained in pyridine and in

concentrated H2SO4 (Table 2). There is a shoulder at the

slightly higher energy sides for all products. Metal-free

phthalocyanine (3) decomposes slowly by hydrolysis in

concentrated H2SO4, which is demonstrated by a decrease

in the absorption coefficient at longer wavelengths. Metal-

containing (4–9), however, were stable. The hydrolytical

decomposition of polymeric phthalocyanines has already

been reported.[5] In order to standardize the UV-Vis spectra,

all samples were stirred in concentrated H2SO4 for 25 min

before the spectra were recorded. As expected, when going

from organic solvents to concentrated H2SO4, the long-

wave absorption band underwent a significant bathochrom-

ic shift, which is due to protonation of the porphyrazine ring

at the meso nitrogen atoms. The intensity of these

absorptions also decreased.

The UV-Vis spectrum of the metal-free phthalocyanine

polymer was obtained in pyridine and concentrated H2SO4.

Figure 2 shows the UV-Vis spectra of a dilute H2SO4

solution and a pyridine suspension of (3). The UV/Vis

absorption spectrum of (3), with minimized scattering

effects, was obtained using a suspension of the material in

pyridine, and showed that, for each network, the primary

band in the visible region (Q-band) was unperturbed by

exciton coupling phthalocyanine units. In the case of an

H2SO4 solution of (3), the primary band in the visible region

was broadened and shifted to longer wavelength (�80 nm).

The intensity ratio of l¼ 236–298 nm and lmax (706–

883 nm) of the Q-bands in the polymeric phthalocyanines

(3–9) can be seen in Table 2. In all cases, the intensities in

the UV (soret band transition) and Vis (Q-band transition)

were IUV/IVis � 1. This result indicates that all of the

polymeric phthalocyanines (3–9) were structurally uni-

form polymers.

The intrinsic viscosities of dilute solutions of the metal-

free and metallophthalocyanine polymers were measured in

concentrated H2SO4 (98 wt.-%) at 25 8C using an Ub-

belohde No.2 viscometer. As can be seen in Table 3, the

intrinsic viscosity of the metal-free polymer was higher

Table 2. Wavelength and absorption coefficients of the UV/Vis spectra of polymeric phthalocyanines.

Compound M Solvent l Ratioa)

UV/Visnm (log e)

(3) 2H Pyridine 706 (3.32), 673 (3.29), 645 (3.01), 609 (2.84), 402 (2.89), 341 (3.37), 326 (3.82),309 (3.81), 268 (3.62)

1.09

H2SO4 794 (4.58), 698 (4.32), 634 (4.28), 610 (4.46), 388 (5.68), 304 (6.28), 292 (6.05),258 (6.36)

1.39

(4) Ni H2SO4 796 (6.65), 706 (6.12), 616 (4.42), 496 (5.74), 306 (6.72), 252 (6.82) 1.02(5) Co H2SO4 800 (5.89), 712 (5.39), 646 (4.75), 612 (4.88), 416 (5.45), 304 (6.19), 298 (6.08) 1.03(6) Fe H2SO4 810 (6.18), 733 (6.24), 618 (6.25), 386 (6.60), 318 (7.01), 270 (6.79) 1.10(7) Pb H2SO4 883 (3.93), 833 (3.85), 739 (4.74), 632 (4.89), 610 (3.83), 485 (4.57), 334 (4.95),

291 (5.26), 278 (5.24)1.33

(8) Cu H2SO4 834 (5.37), 706 (3.90), 622 (5.85), 362 (5.91), 302 (6.24), 254 (6.23), 236 (6.85) 0.86(9) Zn H2SO4 824 (6.40), 726 (5.73), 664 (4.81), 614 (4.97), 502 (5.52), 490 (5.50), 352 (6.12),

308 (6.47), 256 (6.49)1.01

a) Intensity ratio of absorption B-bands at l¼ 236–298 nm and Q-bands at l¼ 706–883 nm. C¼ 3.5� 10�4 g �L�1 in H2SO4,1.0� 10�3 g �L�1 in pyridine.



than the metallophthalocyanine polymers, while the intrin-

sic viscosities of the metallophthalocyanines were very

similar. The higher intrinsic viscosity of the metal-free

phthalocyanine is probably due to easier protonation and a

higher degree of polymerization. Figure 3 shows the visco-

sities of the polymers as a function of polymer concen-

tration. Figure 3 indicates that the viscosities decreased

depending on polymer concentration. This behavior can be

explained by two effects: (1) degradation of the polymers

and (2) weak protonation of the four bridging nitrogen

atoms at the periphery of each phthalocyanine polymer.

The d.c. electrical conductivities of the phthalocyanine

polymers (3a, 3–9) are given in Table 3. They were mea-

sured at room temperature under an argon atmosphere and

in a vacuum in the polycrystalline form as a sandwich

between two gold plates. These values correspond to

semiconductive materials as encountered in number-

substituted phthalocyanine derivatives.[50] The conductiv-

ity values obtained under an argon atmosphere for most of

the phthalocyanine polymers showed an increase of about

ten fold. The enhancement of the conductivity in argon

for the phthalocyanine polymers may be due to absorbed

oxygen in the argon.[51,52] A first approximation to achieve

higher electrical conductivities in phthalocyanines is to

reach partially oxidized states. For this purpose, polymeric

metal-free phthalocyanine (3) was doped with I2 and the

conductivity of the doped product (3a) was approximately

57 times higher than that of the parent compound, (3).

Polymers with a phthalocyanine (Pc) ring are resistant to

thermal oxidation.[53] The thermal properties of metal-free

and metallophthalocyanines were investigated by DSC.

DSC curves exhibited exothermic changes for all polymeric

phthalocyanines (3–9) in the region investigated.[54] The

curves did not show melting points except for 3 (Table 4).

The initial decomposition temperature decreased in the

order (9)> (4)> (5)> (7)> (6)> (8)> (3). Cu-containing

Figure 2. UV-Vis spectra of (3) in pyridine and sulfuric acid.

Table 3. Electrical conductivity and intrinsic viscosities of the polymeric phthalocyanines at room temperature.

Compound M Conductivity Pellet thickness Intrinsic viscosity[Z] (H2SO4)

S � cm�1 mm

in argon in vacuum

(3) 2H 6.85� 10�8 5.87� 10�9 0.60 3.00(3a) 3(I2)n 3.81� 10�7 3.34� 10�7 0.65 –(4) Ni 1.03� 10�7 1.91� 10�8 0.75 1.64(5) Co 2.51� 10�8 8.90� 10�9 0.50 1.28(6) Fe 1.28� 10�7 8.56� 10�8 0.50 1.37(7) Pb 1.65� 10�7 1.26� 10�7 0.40 1.13(8) Cu 2.36� 10�7 5.65� 10�8 0.55 1.27(9) Zn 2.05� 10�7 1.54� 10�7 0.40 1.60

Figure 3. Intrinsic viscosities of polymers.



polymer (8) was the most rapidly degraded metallophth-

alocyanine. On the other hand, Zn- and Ni-containing

metallophthalocyanines showed good thermal stability

under working conditions. These results are in good agre-

ement with the literature.[55] The DSC thermogram of (3a)

shows an endothermic peak at 124 8C due to the dissociation

of iodine. The thermal stability of (3a) was lower than the

undoped analogue (3). The thermal stability of (3a)

indicates that the dopant is rather weakly bonded in the

polymer. Figure 4 shows the DSC thermogram of (3). The

sharpness of the melting point (185 8C) gives an indication

of the purity of compound (3).

The affinity of heavy metal ions for (3) was evaluated by a

biphasic extraction method of the metal picrate from THF

suspensions to the solid metal-free polymer, due to its

insolubility. The complex formation is favorable in apolar

solvents such as THF.[56] The highest extraction affinity of

(3) was determined as 65.4% for Ag1þ. The extraction

affinity of (3) for Hg2þ, Pb2þ, Cd2þ, Cu2þ and Zn2þ were

determined as 40.57, 27.20, 34.11, 48.17 and 6.85%,

respectively. Higher values for Hg2þ, Agþ, Cd2þ and Pb2þ

were expected results. This is because, as reported by

Vujasinovic et al.,[57] sulfur containing ligands are especi-

ally appropriate for complexation with heavy metal ions

such as Hg2þ, Agþ, Cd2þ and Pb2þ due to the softness of

sulfur.

Conclusion

We have synthesized and characterized new p-xylylenebis-

(oxa-thia-propan) bridged metal-free and metallophthalo-

cyanine polymers. The metal-free phthalocyanine polymer

(3) was prepared by the reaction of a tetranitrile monomer

Table 4. Thermal properties of the polymeric phthalocyanines.

Compound M Melting point Dissociation ofiodine, Tmax

Initial decompositiontemperature

Main decompositiontemperature

8C 8C 8C 8C

(3) 2H 185 – 253 292(3a) 3(I2)n – 124 221 269(4) Ni – – 349 477(5) Co – – 334 440(6) Fe – – 321 433(7) Pb – – 325 392(8) Cu – – 305 381(9) Zn – – 415 508

Figure 4. DSC thermogram of (3).



with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in amyl

alcohol. Metallophthalocyanines were prepared by the

reaction of tetranitrile monomer with the chlorides of Ni(II)

and Co(II), the acetates of Cu(II) and Zn(II), yellow PbO and

Fe(CO)5. Co-containing phthalocyanine polymer was

prepared by two different methods. DSC curves of all the

polymers except for (3) exhibited exothermic changes

without any melting point. Zn- and Ni-containing polymers

showed good thermal stability while Cu-containing poly-

mer was the most rapidly degraded. In the case of the DSC

thermogram of iodine doped metal-free polymer, there was

an endothermic peak at 124 8C due to the dissociation of

iodine. The electrical conductivities of the polymeric

phthalocyanines measured as gold sandwiches were found

to be 10�9–10�7 S � cm�1 invacuo and argon. The electrical

conductivity of iodine doped metal-free phthalocyanine

(3a) was found to be approximately 57 times higher than

that of the undoped sample. The extraction ability of (3) was

evaluated in THF using several transition metal picrates,

such as Ag1þ, Hg2þ, Pb2þ, Cd2þ, Cu2þ and Zn2þ, and the

extraction affinity of (3) for Ag1þ was the highest. Intrinsic

viscosities of dilute solutions of metal-free polymer and

metallophthalocyanine polymers were measured in con-

centrated H2SO4 using an Ubbelohde No.2 viscometer. The

intrinsic viscosity of the metal-free polymer was higher

than the metallophthalocyanine polymers while the intrin-

sic viscosities of the metallophthalocyanines were very

similar. The higher intrinsic viscosity of the metal-free

phthalocyanine is probably due to easier protonation and a

higher degree of polymerization.

Acknowledgements: This study was supported by TheScientific and Technical Research Council of Turkey(TUBITAK), Project Number: TBAG-2453(104T065) (Ankara,Turkey). We are indebted to Professor M. Hanack (TubingenUniversity, Germany) and Dr. Beytullah Ertem (KaradenizTechnical University, Turkey) for their assistance with some MSspectral data.

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novel network polymeric phthalocyanines: synthesis and characterization

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