Living cationic polymerization of azobenzene‐containing vinyl ether and its photoresponsive behavior

The living cationic polymerization of 4‐[2‐(vinyloxy)ethoxy]azobenzene (AzoVE) was achieved with various Lewis acids in the presence of an ester as an added base. When Et_1.5AlCl_1.5 was used as a catalyst, the living polymerization system was controllable by UV irradiation as a result of cis and trans isomerization of the azobenzene side groups. Furthermore, an initiating system consisting of SnCl₄ and EtAlCl₂ realized fast living polymerization of AzoVE. The polymerization rate of this system was 3 orders of magnitude faster than that obtained with Et_1.5AlCl_1.5. Poly(4‐[2‐(vinyloxy)ethoxy]azobenzene) was soluble in a diethyl ether/hexane mixture at 25 °C but became insoluble upon irradiation with UV light. This phase‐transition behavior was sensitive and reversible upon irradiation with UV or visible light and reflected the change in polarity occurring with cis and trans isomerization of the azobenzene side groups in the polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5138–5146, 2005     

Synthesis and photoresponsive behavior of azobenzene‐containing side‐chain liquid crystalline diblock polymers with polypeptide block

Well‐defined azobenzene‐containing side‐chain liquid crystalline diblock copolymers composed of poly[6‐(4‐methoxy‐azobenzene‐4′‐oxy) hexyl methacrylate] (PMMAZO) and poly(γ‐benzyl‐L ‐glutamate) (PBLG) were synthesized by click reaction from alkyne‐ and azide‐functionalized homopolymers. The alkyne‐terminated PMMAZO homopolymers were synthesized by copper‐mediated atom transfer radical polymerization with a bromine‐containing alkyne bifunctional initiator, and the azido‐terminated PBLG homopolymers were synthesized by ring‐opening polymerization of γ‐benzyl‐L ‐glutamate‐N‐carboxyanhydride in DMF at room temperature using an amine‐containing azide initiator. The thermotropic phase behavior of PMMAZO‐b‐PBLG diblock copolymers in bulk were investigated using differential scanning calorimetry and polarized light microscopy. The PMMAZO‐b‐PBLG diblock copolymers exhibited a smectic phase and a nematic phase when the weight fraction of PMMAZO block was more than 50%. Photoisomerization behavior of PMMAZO‐b‐PBLG diblock copolymers and the corresponding PMMAZO homopolymers in solid film and in solution were investigated using UV–vis. In solution, trans–cis isomerization of diblock copolymers was slower than that of the corresponding PMMAZO homopolymers. These results may provide guidelines for the design of effective photoresponsive anisotropic materials. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis of azobenzene‐containing polythiophenes and photoinduced anisotropy

Three new polythiophenes containing an azobenzene moiety in the side‐chain were synthesized and characterized. Two of them, which are slightly soluble in tetrahydrofuran to allow the preparation of thin films from solution casting, were used to investigate the photoinduced anisotropy arising from the photoisomerization of azobenzene in this type of polymer. The results show that, unlike other amorphous azobenzene polymers, only an extremely small anisotropy can be induced on excitation with an Ar⁺ laser at 488 nm in these azobenzene‐containing polythiophenes, and that this photoinduced anisotropy is observable only by heating the polymer to some temperatures below glass transition temperature. It is suggested that the inability for azobenzene polythiophenes to display a significant photoinduced anisotropy may be caused by some structural constraints and/or a severe interference from conjugated thiophene chains that absorb strongly in the visible region. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3445–3455, 2004     

A visible light responsive azobenzene‐functionalized polymer: Synthesis,self‐assembly,and photoresponsive properties

A novel visible light responsive random copolymer consisting of hydrophobic azobenzene‐containing acrylate units and hydrophilic acrylic acid units has been prepared. The azobenzene molecule bearing methoxy groups at all four ortho positions is readily synthesized by one‐step conversion of diazotization. The as‐prepared polymer can self‐assemble into nanoparticles in water due to its amphiphilic nature. The tetra‐o‐methoxy‐substituted azobenzene‐functionalized polymer can exhibit the trans‐to‐cis photoswitching under the irradiation with green light of 520 nm and the cis‐to‐trans photoswitching under the irradiation with blue light of 420 nm in both solution and aggregate state. The morphologies of the self‐assembled nanoparticles are revealed by TEM and DLS. The controlled release of loaded molecules from the nanoparticles can be realized by adjusting pH value since the copolymer possesses pH responsive acrylic acid groups. The fluorescence of loaded Nile Red in the nanoparticles can be tuned upon the visible light irradiation. The reversible photoswitching of the azobenzene‐functionalized polymer under visible light may endow the polymer with wide applications without using ultraviolet light at all. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2768–2775     

Synthesis of end‐functionalized polyethers by phosphazene base‐catalyzed ring‐opening polymerization of 1,2‐butylene oxide and glycidyl ether

For the living ring‐opening polymerization (ROP) of epoxy monomers, the catalytic activity of organic superbases, tert‐butylimino‐tris(dimethylamino)phosphorane, 1‐tert‐butyl‐2,2,4,4,4‐pentakis(dimethylamino)‐2Λ⁵,4Λ⁵‐catenadi(phosphazene), 2,8,9‐triisobutyl‐2,5,8,9‐tetraaza‐1‐phosphabicyclo[3.3.3]undecane, and 1‐tert‐butyl‐4,4,4‐tris(dimethylamino)‐2,2‐bis[tris(dimethylamino)phosphoranylidenamino]‐2Λ⁵,4Λ⁵‐catenadi(phosphazene) (t‐Bu‐P₄), was confirmed. Among these superbases, only t‐Bu‐P₄ showed catalytic activity for the ROP of 1,2‐butylene oxide (BO) to afford poly(1,2‐butylene oxide) (PBO) with predicted molecular weight and narrow molecular weight distribution. The results of the kinetic, post‐polymerization experiments, and MALDI‐TOF MS measurement revealed that the t‐Bu‐P₄‐catalyzed ROP of BO proceeded in a living manner in which the alcohol acted as the initiator. This alcohol/t‐Bu‐P₄ system was applicable to the glycidol derivatives, such as benzyl glycidyl ether (BnGE) and t‐butyl glycidyl ether, to afford well‐defined protected polyglycidols. The α‐functionalized polyethers could be obtained using different functionalized initiators, such as 4‐vinylbenzyl alcohol, 5‐hexen‐1‐ol, and 6‐azide‐1‐hexanol. In addition, the well‐defined cyclic‐PBO and PBnGE were successfully synthesized using the combination of t‐Bu‐P₄‐catalyzed ROP and click cyclization. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

The First Example of Main‐Chain Cyclic Azobenzene Polymers

A novel main‐chain azobenzene cyclic polymer, cyclic‐PEHPA, has been successfully synthesized by ‘click’ cyclization of the α‐alkyne‐ω‐azido hetero‐difunctional linear precursors (linear‐PEHPA), which is synthesized by a step‐growth polymerization of the 3′‐ethynylphenyl[4‐hexyl‐(2‐azido‐2‐methyl‐ propionate) phenyl] azobenzene (EHPA). Gel permeation chromatography, and ¹H NMR and FT‐IR spectra confirmed the complete transformation of linear‐PEHPA into cyclic‐PEHPA. With the same molecular weights, the cyclic‐PEHPAs are found to have higher glass transition temperatures than the linear‐PEHPAs, but almost the same decomposition temperatures. In addition, the obtained cyclic azobenzene polymer with lower molar mass shows a slightly better trans–cis–trans photoisomerization ability than the corresponding linear‐PEHPA.

     

Vinyl‐terminated side‐chain liquid‐crystalline polyethers containing mesogenic benzylideneaniline moieties

The synthesis of two vinyl‐terminated side‐chain liquid‐crystalline polyethers containing benzylideneaniline moieties as mesogenic cores was approached in two different ways: by chemically modifying poly(epichlorohydrin) with suitable mesogenic acids or by polymerizing analogous glycidyl ester or glycidyl ether derivatives. In all the conditions tested, the first approach led to materials in which the imine group was hydrolyzed. The second approach led to the desired polymers PG2a and PG2b , but only from the glycidyl ether derivatives and when the initiator was the system that combined polyiminophosphazene base t‐Bu‐P₄ and 3,5‐di‐t‐butylphenol. These polymers were chemically characterized by IR and ¹H and ¹³C NMR spectroscopies. The estimated degrees of polymerization ranged from 30 to 36. The liquid crystalline behavior of the synthesized polymers was studied by differential scanning calorimetry, polarized optical microscopy (POM) and X‐ray diffraction. Both polymers behave like liquid crystals and exhibited a single mesophase, which was recognized as a smectic C mesophase, probably with a bilayer arrangement, i.e., a smectic C₂ mesophase. The crosslinking of both polymers was performed with dicumyl peroxide as initiator, which led to liquid crystalline thermosets. POM and X‐ray diffraction confirmed that the mesophase organization mantained on the crosslinked materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1877–1889, 2006     

Synthesis and isomerization of conjugated oligomers containing azoimidazole unit

The Suzuki (for O1 – O3 ) and Stille (for O4 ) coupling polymerization of 2‐(phenylazo)imidazole bearing the benzyl protecting group at the 1‐position gave conjugated oligomers. The transformation from the neutral imidazole in the conjugated oligomer O2 , consisted of the alternating 2,5‐didecyl‐1,4‐phenylene unit, to the cationic imidazolium salt O2S was performed. Depending on the chemical structure of coupling partners, the absorption maximum of conjugated oligomers showed red shift or blue shift from that of the model compound M with the benzene ring at the 4,5‐positions. The absorption maximum wavelength of the cationic conjugated oligomer O2S showed a blue shift from that of the neutral conjugated oligomer O2 . The trans‐to‐cis photoisomerization of the azoimidazole unit in conjugated oligomers was observed by irradiating the light at 436 nm, and the conversion degree to the cis structure had a rough correlation with the maximum absorption wavelength of materials. The trans‐to‐cis photoisomerization in the film state was sluggish. On the other hand, the cis‐to‐trans thermal isomerization of the azoimidazole unit was confirmed and the absorbance returned to the initial state before the photoisomerization. The trans‐to‐cis photoisomerization of the cationic conjugated oligomer O2S required large energy, and the prolonged light irradiation might decompose the azoimidazole unit. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Bis‐hydrophilic and functional triblock terpolymers based on polyethers: Synthesis and self‐assembly in solution

A well‐defined triblock terpolymer, poly(ethylene glycol)‐block‐poly(allyl glycidyl ether)‐block‐poly(tert‐butyl glycidyl ether) (PEG‐b‐PAGE‐b‐Pt‐BGE), with a narrow molar mass distribution has been synthesized by sequential living anionic ring‐opening polymerization. Afterward, the PAGE block was modified via thiol‐ene chemistry and different sugar moieties or cysteine as a model compound for peptides could be covalently attached to the polymer backbone. The solution self‐assembly of the obtained bis‐hydrophilic triblock terpolymers in aqueous media has been studied in detail by turbidimetry, dynamic light scattering, and transmission electron microscopy (TEM and cryo‐TEM). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Phase behavior and photo‐responsive studies of photoactive liquid crystalline hyperbranched polyethers containing benzylidene moiety

Two sets of hyperbranched polyether epoxies were synthesized to study the effect of substituent, rigidity, and nature of photoactive unit on the thermal and photoresponsive properties. Each set was comprised of one molecule with an acyclic moiety in the repeating unit, and two molecules with a cyclic moiety of varying rigidity (cycle size) in the repeating unit. Two substituents on aromatic rings in the repeating unit were present in one set, and other set was without a substituent. The mesogenic and photoresponsive properties were studied and correlated to the varied structural parameters. The effects of varied molecular structural parameters on phase behavior and photoresponsive properties were very prominent. Out of six monomeric diols, only four have exhibited liquid crystalline phase while the polymers corresponding to all monomeric diols revealed mesophase. The findings in photoresponsive properties were further supported by molecular modeling studies. The changes in refractive index, photoviscosity, and fluorescence intensity with irradiation time substantiated the spectral pattern observed in UV‐Vis spectroscopy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2774–2786, 2009     

Synthesis and polymerizability of CN monomers

The synthesis and polymerizability of imine C?N monomers is surveyed. The investigated imines were either far more reactive than similarly substituted C?C or C?O monomers, or too stable to polymerize. Imines with electron‐attracting substituents on N favor polymerization by anionic mechanism, but led only to low molecular weight polymers. Imines with a donor substituent on N, such as N‐arylmethyleneimines, polymerized by cationic or anionic mechanism. 1‐ and 2‐Aza‐1,3‐butadienes were also rather unstable and polymerized to oligomers. The symmetrically substituted 2,3‐diaza‐1,3‐butadienes could be purified and polymerized successfully using anionic initiators, resulting in both 1,4‐ and 1,2‐structures in the polymer backbone, depending on the substituents. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of azobenzene‐containing polymers via RAFT polymerization and investigation on intense fluorescence from aggregates of azobenzene‐containing amphiphilic diblock copolymers

The well‐defined azobenzene‐containing homopolymers, poly{6‐(4‐phenylazophenoxy)hexyl methacrylate (AHMA)} (PAHMA), were synthesized via reversible addition fragmentation chain transfer polymerization (RAFT) in anisole solution using 2‐cyanoprop‐2‐yl 1‐dithionaphthalate (CPDN) as the RAFT agent and 2,2′‐azobisisobutyronitrile (AIBN) as the initiator. The first‐order kinetic plot of the polymerization and the linear dependence of molecular weights of the homopolymers with the relatively low polydispersity index values (PDIs ≤ 1.25) on the monomer conversions were observed. Furthermore, the amphiphilic diblock copolymer, poly{6‐(4‐phenylazophenoxy)hexyl methacrylate (AHMA)}‐b‐poly{2‐(dimethylamino)ethyl methacrylate (DMAEMA)} (PAHMA‐b‐PDMAEMA), was prepared with the obtained PAHMA as the macro‐RAFT agent. The structures and properties of the polymers were characterized by ¹H NMR and GPC, respectively. Interestingly, the amphiphilic diblock copolymers in chloroform (CHCl₃) solution (PAHMA₂₃‐b‐PDMAEMA₉₇ (4 × 10^?5 M, M_n(GPC) = 18,400 g/mol, PDI = 1.48) and PAHMA₂₈‐b‐PDMAEMA₁₁₇ (6 × 10^?5 M, M_n(GPC) = 19,300 g/mol, PDI = 1.51) exhibited the intense fluorescence emission at ambient temperature. Moreover, the fluorescent intensity of PAHMA‐b‐PDMAEMA in CHCl₃ was sensitive to the ultraviolet irradiation at 365 nm, which increased within the first 10 min and later decreased when irradiation time was prolonged to 30 min or longer. The well distributed, self‐assembled micelles composed of azobenzene‐containing amphiphilic diblock copolymers, (PAHMA‐b‐QPDMAEMA)s (QPDMAEMA is quaternized PDMAEMA), in the mixed N,N‐dimethyl formamide (DMF)/H₂O solutions were prepared. Their fluorescent intensities decreased with the increasing amount of water. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5652–5662, 2008     

Synthesis of medium‐bandgap π‐Conjugated polymers based on isomers of 5‐Alkylphenanthridin‐6(5H)‐one and 6‐Alkoxylphenanthridine

Two novel dibromo monomers consisting of the isomers of 5‐alkylphenanthridin‐6(5H)‐one (PN) and 6‐alkoxylphenanthridine (PO) were synthesized through alkylation of the precursor 3,8‐dibromophenanthrindi‐6(5H)‐one, where the molecular structures were confirmed by NMR spectroscopy. The medium bandgap conjugated polymers PDBTPN and PDBTPO were constructed by utilizing such two isomers PN and PO as the electron‐donating units and dithiophenebenzo[2,1,3]diathiazole as the electron‐accepting unit. The resulting polymers exhibited analogous absorption profiles with optical bandgap of 1.90 eV, while PDBTPO showed slightly higher absorption coefficiency. Cyclic voltammetry measurements revealed that these polymers had relatively deep highest occupied molecular orbital levels of about ?5.70 eV. Polymer solar cells based on such two polymers showed relatively high open‐circuit voltage of about 0.90 V. All devices exhibited moderate performances with the best power conversion efficiency of 3.77% achieved based on PDBTPO. Devices based on PDBTPO showed slightly higher power conversion efficiency than those based on PDBTPN, which can be ascribed to higher hole mobility and more favorable film morphology of the former. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2119–2127     

Controlled grafting of ethyl cellulose with azobenzene‐containing polymethacrylates via atom transfer radical polymerization

Graft copolymers of ethyl cellulose with azobenzene‐containing polymethacrylates were synthesized through atom transfer radical polymerization (ATRP). The residual hydroxyl groups on ethyl cellulose were first esterified with 2‐bromoisobutyryl bromide to yield 2‐bromoisobutyryloxy groups, which was then used to initiate the polymerization of 6‐[4‐(4‐methoxyphenylazo)phenoxy]hexyl methacrylate (MMAzo) in the presence of CuBr/N,N,N′,N″,N″‐pentamethylenetriamine (PMDETA) as catalyst and anisole as solvent. The graft copolymers were characterized by gel permeation chromatography (GPC) and ¹H‐NMR. The molecular weights of the graft copolymers increased relatively to the macroinitiator, and the polydispersities were narrow. The thermal and liquid crystalline property of the graft copolymers were investigated by differential scanning calorimeter (DSC) and polarizing optical microscope (POM). Photoresponsive property was studied under the irradiation of UV–vis light in THF solution. The graft copolymers have potential applications, including sensors and optical materials. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1653–1660, 2007     

Photomechanical effects in liquid crystal polymer networks prepared with m‐fluoroazobenzene

The photomechanical response and photochemistry of a conventional, unsubstituted azobenzene‐functionalized liquid crystalline polymer network (azo‐LCN) is contrasted to that of an analogous material prepared with meta‐fluorinated azobenzene chromophores. The polydomain azo‐LCN materials exhibit nearly identical thermomechanical and optical properties. Photomechanical characterization indicates that the fluorination of the azobenzene chromophore reduces the deflection of cantilevers composed of the materials by 50%, which spectroscopic analysis reveals is due to a reduction in the ability of this material to isomerize and potentially reorient. This work is further confirmation that the underlying photochemistry of azobenzene is a primary contributor to the generation of photomechanical work in these materials. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 876–882     

Optical‐limiting and nonlinear optical polyacetylenes: Synthesis of azobenzene‐containing poly(1‐alkyne)s with different spacer and tail lengths

Poly(1‐alkyne)s containing azobenzene pendant groups with different lengths of the spacer and terminal alkyloxy group {? [HC?C(CH₂)_mOCO? C₆H₄? N?N? C₆H₄? OC_pH_2p+1]_n? , where m = 1, 2, 3, or 9 and p = 4, 7, or 12} were synthesized in satisfactory yields with the [Rh(nbd)Cl]₂–Et₃N catalyst. All the polymers were soluble in common organic solvents such as CHCl₃ and tetrahydrofuran. Their structures and properties were characterized and evaluated with IR, NMR, thermogravimetric analysis, UV, and optical‐limiting and nonlinear optical analyses. All the polymers were thermally stable and decomposed at temperatures as high as ～300 °C. The optical‐limiting and nonlinear optical properties of the polymers were sensitive to their molecular structures. Polymers having shorter spacer lengths and longer terminal groups showed better performances and larger third‐order nonlinear optical susceptibility (up to 1.34 × 10^?10 esu). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2346–2357, 2006     

Synthesis and characterization of an azobenzene‐ and acrylamide‐based photoresponsive copolymer and gel

This article reports the synthesis and characterization of a new type of copolymer consisting of acrylamide and trans‐4‐methacroyloxyazobenzene and their gel. Free‐radical polymerization initiated with 2,2′‐azobisisobutyronitrile was used to conduct the synthesis although N,N′‐methylene bisacrylamide was used as a crosslinking agent for the gel synthesis. Despite the insolubility of the different monomers in a single solvent, a certain ratio of water/tetrahydrofuran (THF) enabled the propagating species to stay in the solution and thus to facilitate chain growth. The solubility, Fourier transform infrared spectra, and solid‐state ¹³C NMR investigations revealed that two monomers in the copolymer were chemically bonded. The compositions of the incorporated acrylamide and azobenzene in the copolymer and the gel were determined by NMR spectroscopy. Because the potential actuating behavior of such materials was due to the volume change involved in reversible solvent uptake, the sorption and evaporation of the gel were also investigated and showed that the gel could absorb about 460% water, which corresponded to a polymer content of the weight gel of 18% and was compatible with thermogravimetric analysis of a saturated gel that revealed about 83 wt % of a swollen gel was lost within 12 h. Finally, photoinduced trans–cis isomerization kinetics of the copolymer was investigated in a 30:70 mixture of water and THF against irradiation time. A photostationary state was reached within 5.5 min with a corresponding conversion of 70% of the trans isomer to the cis form. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2886–2896, 2004     

Molecularly imprinted polymers bearing spiropyran‐based photoresponsive binding sites capable of photo‐triggered switching for molecular recognition activity

Photoresponsive molecularly imprinted nanocavities were prepared using a newly designed functional monomer bearing a photoresponsive spiropyran moiety with a carboxy group that can interact with atrazine (the template molecule), in which the spiropyran moiety was incorporated into the binding cavities. Spectrophotometric analysis confirmed that the spiropyran moiety was photoresponsive even after polymerization. The selectivity of the EDMA‐based molecularly imprinted polymer (MIP_EDMA) was tested to examine the binding behavior of atrazine and other agrochemicals, revealing that the atrazine‐imprinted polymer can bind selectively to triazine herbicides. Photo‐triggered switching of the binding activity in MIP_EDMA was investigated, and the binding activity was found to decrease dramatically after UV light irradiation, suggesting that the spiropyran moiety in the binding cavities was transformed to the merocyanine form, resulting in unfavorable translocation of the carboxy group for atrazine binding. Consequently, the spiropyran‐based MIP_EDMA demonstrated in this study could open a way to realizing reliable photoresponsive smart materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1637–1644     

Thermoresponsive Copolymers of Ethylene Oxide and N,N‐Diethyl Glycidyl Amine: Polyether Polyelectrolytes and PEGylated Gold Nanoparticle Formation

The synthesis of diblock as well as gradient copolymers of N,N‐diethyl glycidyl amine (DEGA) with ethylene oxide (EO) via anionic ring‐opening polymerization is presented. The polymers exhibit low polydispersities (≤1.13) and molecular weights in the range of 3300–10 200 g mol⁻¹. In PEG‐co‐PDEGA copolymers, incorporation of 4%–29% DEGA results in tailorable cloud point temperatures in aqueous solution and melting points depending on DEGA content. mPEG‐b‐PDEGA block copolymers can be quaternized to generate cationic double‐hydrophilic polyelectrolyte copolymers with polyether backbone. Furthermore, mPEG‐b‐PDEGA has been used as dual reducing and capping agent for gold nanoparticle synthesis.     

Synthesis,characterization, and electrical properties of a diazodiphenylene‐bridged Cu–phthalocyanine polymer

A diazodiphenylene‐bridged Cu–phthalocyanine polymer was synthesized from the diazonium salt of bensidine and the Cu(II) 1,8,15,22‐tetraaminophthalocyanine complex and characterized with Fourier transform infrared, ultraviolet–visible spectroscopy, and elemental analysis. The polymer was partially soluble in organic solvents such as dimethylformamide and tetrahydrofuran. The molecular weight of the soluble part of the polymer was investigated with ebullioscopy and viscosimetry methods in tetrahydrofuran. Both methods showed that the molecular weight of the polymer was much larger than that of the complex. The conductivity of the samples was measured with a four‐prop conductivity measuring device. Iodine and hydrogen chloride were doped to the polymer, and an increase of about 10⁴ S cm^?1 in the electrical conductivity was observed. The cyclic voltammogram of the diazodiphenylene‐bridged Cu–phthalocyanine polymer in contact with a LiClO₄ electrolyte exhibited two reductions and two reoxidations with high reversibility and electrochemical stability. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5692–5698, 2006