Synthesis of conjugated polymers with pendant ruthenium terpyridine trithiocyanato complexes and their applications in heterojunction photovoltaic cells

Two conjugated polymers based on poly(phenylenethiophene) and poly (fluorenethiophene) main chain functionalized with pendant trithiocyanato ruthenium terpyridine complexes were synthesized by the Suzuki coupling reaction. The ruthenium complexes can extend the absorption band to longer wavelength and enhance the photosensitivity in this region. The polymers exhibit very broad absorption band spanning from 400 to 750 nm due to the presence of π‐conjugated system and the ruthenium complexes. Such enhancement in optical absorption enables the utilization of solar light in the near IR region. By space charge limited current modeling, the hole carrier mobilities of the polymers were calculated to be in the order of 10^?4 cm² V^?1 s^?1, which greatly facilitate the transport of charges after the separation of excitons. Heterojunction photovoltaic cells with simple structure ITO/polymer/C₆₀/Al were fabricated. Under simulated AM1.5 solar light illumination, the short circuit currents, open circuit voltages, and power conversion efficiencies of the photovoltaic cells were measured to be 1.53–2.58 mA cm^?2, 0.12–0.24 V, and 0.084–0.12%, respectively. Deposition of PEDOT:PSS on ITO surface did not show significant difference in device performance. Plot of incident photon to charge efficiency as the function of wavelength suggests that absorption by both conjugated main chain and ruthenium complex are essential to the photocurrent generation. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1305–1317, 2008     

Synthesis of optically active polymers containing chiral phosphorus atoms in the main chain

We successfully synthesized optically active polymers by using a chiral bisphosphine, (S,S)‐1,2‐bis[boranato(t‐butyl)methylphosphino]ethane, as a key building block. Their structures were characterized with ¹H, ¹³C, and ³¹P NMR spectra. The obtained polymers exhibited different glass‐transition temperatures depending on the structure of each comonomer, whereas a model compound had a melting point. According to circular dichroism spectra, the difference in the stereochemistry of the comonomers yielded the different higher‐ordered structures of the polymers induced by chiral phosphine units. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 866–872, 2007     

Synthesis and characterization of new π‐conjugated polymers containing 1,8‐naphthyridine in the main chain: Role of the 1,8‐naphthyridine unit in π‐conjugated polymers

Alternating π‐conjugated copolymers of 1,8‐naphthyridine‐2,6‐diyl ( 1,8‐Nap ) with 9,9‐dioctylfluorene‐2,7‐diyl ( P(Flu‐Ph‐1,8‐Nap) ) and 2,5‐didodecyloxy‐1,4‐phenylene ( P(ROPh‐Ph‐1,8‐Nap) ) have been synthesized by Pd‐catalyzed organometallic polycondensation. The copolymers showed UV‐vis absorption peaks at around 390 nm in o‐dichlorobenzene. The polymers were photoluminescent both in o‐dichlorobenzene and in the solid state. In o‐dichlorobenzene, the emission peaks of P(Flu‐Ph‐1,8‐Nap) and P(ROPh‐Ph‐1.,8‐Nap) appeared at λ_EM = 440 and 471 nm, with quantum yields of 87% and 66%, respectively. Electrochemical data revealed that 1,8‐Nap behaved as a typical electron‐accepting unit. When P(Flu‐Ph‐1,8‐Nap) was treated with 10‐camphorsulfonic acid, the emission peak shifted to λ_EM = 598 nm. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Tuning the electronic properties of conjugated polymer by tethering low‐bandgap rhenium(I) complex on the main chain

Low‐bandgap rhenium(I) complex with absorption onset at 795 nm in solution was tethered onto π‐conjugated polymer. The conjugated copolymer provides solution processability of the metallopolymer, and the pendant allows the low energy‐absorbing Re(I) complex units to be evenly distributed on the thin film. The copolymer tethered with low‐bandgap rhenium complex was synthesized by Suzuki cross‐coupling reaction. The metal‐free polymer ( poly‐1 ) tethered with functionalized intramolecular charge transfer dye, 2‐phenyl‐3‐pyridin‐2‐yl‐5,7‐di‐2‐thienylthieno[3,4‐b]pyrazine, exhibited high molecular weight, good film‐forming properties, and excellent solution processability. The pendants of the conjugated polymer possess donor–acceptor characters and broaden the absorption band. These pendants can function as bidentate ligands for metal chelation. The solubilizing groups on the monomers provide good solubility to the polymer even with high content of metal chelation. Upon the complexation with rhenium(I) pentacarbonyl chloride, the absorption spectrum of the resulting metallopolymer was further extended toward the near‐infrared region. Photovoltaic performances based on this metallopolymer have been studied. The design approach of these metallopolymers provides synthetic feasibility for coordinating wide range of metal ions on the pendant, and the resulting low‐bandgap polymer can be a potential candidate for light harvesting material in solar cell applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2311–2319, 2010     

Synthesis of π‐conjugated polymer containing both thiophene and phosphole sulfide in the main chain by simultaneous post‐element transformation of organotitanium polymer

The synthesis and unique optoelectronic features of a π‐conjugated polymer containing both thiophene and 1‐phenylphosphole sulfide units (multiple heteroles) in the main chain by the post‐element transformation of a regioregular organometallic polymer possessing titanacyclopentadiene‐2,5‐diyl unit are described. The π‐conjugated polymer containing multiple heteroles was obtained in 73% yield by the simultaneous reaction of the organotitanium polymer with sulfur monochloride and dichlorophenylphosphine (0.6 equiv each), whose number‐average molecular weight (M_n) and the molecular‐weight distribution (M_w/M_n) were estimated to be 11,000 and 3.4, respectively, by the size exclusion chromatography (SEC). The π‐conjugated polymer thus obtained was found to have the high HOMO and the low LUMO energy levels due to the electron‐rich thiophene and electron‐deficient phosphole sulfide units, respectively, as supported by its cyclic voltammetry (CV) analysis. Compared to a mixture of a polymer containing sole thiophene‐unit and that containing sole phosphole sulfide units, the π‐conjugated polymer‐containing multiple heteroles proved to exhibit interesting optical properties. For example, a specific emission peak was observed at 608 nm in the photoluminescence spectrum, which was not observed in the case of the thiophene‐containing polymer, the phosphole‐containing polymer, and their mixture. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2519–2525     

Synthesis of imidazole‐terminated hyperbranched polymers with POSS‐branching points and their pH responsive and coordination properties

An imidazole‐terminated hyperbranched polymer with octafunctional POSS branching units denoted as POSS‐HYPAM‐Im was prepared by the polymerization of excess amounts of tris(2‐aminoethyl)amine with the first‐generation methyl ester‐terminated POSS‐core poly(amidoamine)‐typed dendrimer, reacting with methyl acrylate, and ester‐amide exchange reaction with 3‐aminopropylimidazole. The imidazole‐terminated hyperbranched poly(amidoamine) denoted as HYPAM‐Im was also synthesized with 1‐(3‐aminopropyl)imidazole from a methyl ester‐terminated hyperbranched poly(amidoamine) by the ester‐amide exchange reaction. The transmittance of the POSS‐HYPAM‐Im solution drastically decreased when the solution pH was greater than 8.2. On the other hand, the transmittance of the HYPAM‐Im solution gradually decreased when the solution pH at 8.5 and was greater than 9. Spectrophotometric titrations of the hyperbranched polymer aqueous solutions with Cu²⁺ ions indicated the variation of the coordination modes of POSS‐HYPAM‐Im from the Cu²⁺–N₄ complex to the Cu²⁺–N₂O₂ complex and the existence of the only one complexation mode of Cu²⁺–N₄ between Cu²⁺ ion and HYPAM‐Im with increasing the concentrations. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2695–2701     

Dithienobenzimidazole‐containing conjugated donor–acceptor polymers: Synthesis and characterization

The synthesis of two new conjugated polymers based on the relatively under‐exploited monomer, 5,8‐dibromo‐2‐[5‐(2‐hexyldecyl)‐2‐thienyl]‐1H‐dithieno[3,2‐e:2′,3′‐g]benzimidazole (dithienobenzimidazole, DTBI ), and either 4,7‐bis[4‐hexyl‐5‐(trimethylstannyl)‐2‐thienyl]‐2,1,3‐benzothiadiazole ( BTD ) or 2,6‐bis(trimethylstannyl)‐4,8‐bis(5‐(2‐ethylhexyl) thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene ( BDT ) is described. The polymers were synthesized via Stille polycondensation and characterized by traditional methods (¹H NMR, gel‐permeation chromatography, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, thermal gravimetric analysis, differential scanning calorimetry, ultraviolet–visible spectroscopy, photoluminescence, and cyclic voltammetry). Prior to their synthesis, trimer structures were modeled by DFT calculations facilitating a further understanding of the systems' electronic and geometric structure. Polymers were titrated with acid and base to take advantage of their amphiprotic imidazole moiety and their optical response monitored with ultraviolet–visible spectroscopy. Finally, pristine polymer thin‐films were treated with acid and base to evaluate (de)protonation's effect on system electronics, but thin‐film degradation was encountered. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 60–69     

Synthesis and characterization of soluble conjugated polymers having pyrene moiety in the main chain

Three new alternating conjugated polymers consisting of pyrene and 3‐dodecylthiophene ( PPyMT ), 4,4′‐didodecyl‐2,2′‐bithiophene ( PPyBT ), or 9,9‐didodecylfluorene ( PPyFlu ) moieties have been prepared using Suzuki coupling reaction or Sugimoto approaches. The polymers were readily soluble in common organic solvents and exhibited good thermal stability in nitrogen and air atmospheres. The structures and optical properties of the polymers were characterized by NMR, FTIR, XRD, UV–vis, and fluorescence spectroscopy. PPyMT and PPYBT showed blue‐light emission in solution, whereas PPyFlu performed blue‐light emitting in film state. The polymers exhibited an intermolecular aggregation and structural ordering due to pyrene–pyrene π–π stacking interaction. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Novel two‐dimensional donor–acceptor conjugated polymers containing quinoxaline units: Synthesis,characterization, and photovoltaic properties

Novel two‐dimensional donor–acceptor (D–A) structured conjugated polymers, P1–P4, were designed and synthesized by introducing electron‐deficient quinoxaline as core and electron‐rich alkoxyl‐phenylenevinylene in side chains and p‐phenylenevinylene, triphenylamine, or thiophene in main chain. Benefited from the D–A structures, the polymers possess low bandgaps of 1.75 eV, 1.86 eV, 1.59 eV, and 1.58 eV for P1, P2, P3, and P4, respectively, and show broad absorption band in the visible region: the shorter wavelength absorption peak at ～400 nm ascribed to the conjugated side chains and the longer wavelength absorption peak between 500 nm and 750 nm belonging to the absorption of the conjugated main chains. Especially, the absorption band of P4 film covers the whole visible range from 300 nm to 784 nm. The power conversion efficiencies of the polymer solar cells based on P1–P4 as donor and PCBM as acceptor are 0.029%, 0.14%, 0.46%, and 0.57%, respectively, under the illumination of AM 1.5, 100 mW/cm². The polymers with the low bandgap and broad absorption band are promising photovoltaic materials. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4038–4049, 2008     

Synthesis and optical and electrochemical properties of new π‐conjugated 1,3,5‐triazine‐containing polymers

Two new π‐conjugated polymers containing 1,3,5‐triazine units in the main chain, Pa and Pb , are reported. Pa and Pb (R = H and ? OCH₃, respectively) showed blue photoluminescence emissions with quantum yields of more than 50% in toluene. In the solid state, Pa and Pb showed photoluminescence maximum emission peaks at 479 and 475 nm, respectively. Electrochemically, Pa and Pb showed good stability and reversibility under repeated electrochemical reduction. The polymers had glass‐transition temperatures higher than 90 °C and had 5 wt % loss temperatures higher than 400 °C. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6554–6561, 2005     

Synthesis and properties of conjugated polymers containing 3,9‐carbazolylene and silylenevinylene moieties in the main chain

Novel conjugated polymers containing 3,9‐carbazolylene and silylenevinylene moieties were synthesized by the hydrosilylation polymerization of 1,4‐bis(3‐ethynyl‐9‐carbazolyl)benzene ( 1 ) with various bis(hydrosilane)s or dihydrosilanes using a rhodium catalyst. Polymers with weight‐average molecular weights ranging from 5400 to 20,000 were obtained in 55–97% yields by the polyaddition with a rhodium catalyst in toluene at 25 °C for 24 h. All the polymers were soluble in CHCl₃ and THF, and had predominantly trans‐structures. The polymers exhibited λ_max at a longer wavelength region than 1 , and emitted fluorescence in 14–50% quantumn yields. The polymers were oxidized and reduced in the region of 0.4–1.6 V, and thermally stable up to 200 °C under air. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1815–1821, 2010     

Tropone‐containing π‐conjugated polymers: Annulation of tropone onto benzene ring in the conjugated polymer

Tropone‐fused, various π‐conjugated polymers ( P2 – P5 ) were synthesized by the palladium‐catalyzed coupling reaction of 1,4‐dibromo‐6,8‐dimethyl‐7H‐benzocyclohepten‐7‐one with aromatic divinyl, diboronic acid, and diethynyl compounds. The molecular orbital calculation of the model compounds was performed to discuss effective conjugation length of the repeating unit of the polymers. The absorption spectra of phenylenevinylene‐type polymers shifted to longer wavelengths than the model compounds by about 60 nm. They exhibited green fluorescence [λ_max(em) = 544 and 561 nm]. The absorption spectrum of a phenylene‐type polymer blueshifted by 10 nm; however, that of a phenyleneethynylene‐type polymer redshifted by 83 nm as compared with their model compounds. They showed fluorescence with peak maxima at 457 and 489 nm, respectively. As a result, the absorption spectra of phenylene‐ and phenylenevinylene‐type polymers blueshifted, but that of a phenyleneethynylene‐type polymer redshifted by the annulation of tropone onto a benzene ring in the conjugated polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1208–1215, 2004     

A novel type of optically active helical polymers: Synthesis and characterization of poly(N‐propargylureas)

This article presents two novel artificial helical polymers, substituted polyacetylenes with urea groups in side chains. Poly( 4 ) and poly( 5 ) can be obtained in high yields (≥97%) and with moderate molecular weights (11,000–14,000). Poly( 4 ) contains chiral centers in side chains, and poly( 5 ) is an achiral polymer. Both of the two polymers adopted helical structures under certain conditions. More interestingly, poly( 4 ) exhibited large specific optical rotations, resulting from the predominant one‐handed screw sense. The helical conformation in poly( 5 ) was stable against heat, while poly( 4 ) underwent conformational transition from helix to random coil upon increasing temperature from 0 to 55 °C. Solvents had considerable influence on the stability of the helical conformation in poly( 4 ). The screw sense adopted by the helices was also largely affected by the nature of the solvent. Poly( 4 ‐co‐ 5 )s formed helical conformation and showed large optical rotations, following the Sergeants and Soldiers rule. By comparing the present two polymers (with one ? N? H groups) with the three polymers previously reported (with two ? N? H groups in side chains), the nature of the hydrogen bonds formed between the neighboring urea groups played big roles in the formation of stable helical conformation. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4112–4121, 2008     

Synthesis and properties of conjugated polymers containing 3,9‐ and 2,9‐linked carbazole units in the main chain

Novel conjugated polymers containing 3,9‐ or 2,9‐linked carbazole units in the main chain were synthesized by the polycondensation of ethynyl‐ and iodo‐substituted 9‐arylenecarbazolylene monomers, and their optical and electrical properties were studied. Polymers with weight‐average molecular weights of 3400–12,000 were obtained in 76–99% yields by the Sonogashira coupling polycondensation in piperidine or tetrahydrofuran (THF)/piperidine at 30 °C for 48 h. All the 3,9‐linked polymers absorbed light around 300 nm. The para‐phenylene‐linked polymer also absorbed light around 350 nm, while meta‐phenylene‐linked one did not. The 3,9‐linked polymers absorbed light at a wavelength longer than the 2,9‐linked one. The polymers emitted blue fluorescence with high quantum yields (0.21–0.78) upon excitation at the absorption maxima. The polymers were oxidized around 0.6 V, and reduced around 0.5 V. Poly( 1 ) showed the dark conductivity of 3.7 × 10^?11 S/cm (10³ V/cm). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3506–3517, 2009     

Synthesis and characterization of alt‐bipyridinylene‐phenylene copolymers containing ruthenium(II) complexes

Poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3a ), poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐4,4′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3b ), and poly{bis(2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3c ) were synthesized by the Suzuki coupling reaction. The alternating structure of the copolymers was confirmed by ¹H and ¹³C NMR and elemental analysis. The polymers showed, by ultraviolet–visible, the π–π* absorption of the polymer backbone (320–380 nm) and at a lower energy attributed to the d–π* metal‐to‐ligand charge‐transfer absorption (450 nm for linear 3a and 480 nm for angular 3b ). The polymers were characterized by a monomodal molecular weight distribution. The degree of polymerization was approximately 8 for polymer 3b and 28 for polymer 3d . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2911–2919, 2004     

High‐efficiency,electrophosphorescent polymers with porphyrin–platinum complexes in the conjugated backbone: Synthesis and device performance

A series of soluble, conjugated, electrophosphorescent copolymers with (meso‐tetraphenylporphyrinato‐κ⁴N)platinum(II) (PtTPP) complexes incorporated into the polymer main chain were synthesized through the copolymerization of narrow‐band‐gap monomeric porphyrin–platinum(II) complexes and wide‐band‐gap dialkyl‐substituted fluorene monomers by a modified Suzuki coupling reaction. The study of the photoluminescence decay indicated that poly[2,7‐(9,9‐dioctylfluorene)‐co‐2,12‐((meso‐tetraphenylporphyrinato‐κ⁴N)platinum(II))] (PFO–PtTPP) was a triplet emitter. The electroluminescence emission from the fluorene segment was completely quenched for copolymers with PtTPP contents as low as 0.5 mol %. The PFO–PtTPP copolymers emitted deep red light. The device based on the porphyrin–platinum(II) copolymer PFO–5PtTPP (with 5 mol % PtTPP in the copolymer) showed the highest external quantum efficiency of 1.95% with an emission peak at 684 nm in an indium tin oxide/poly(3,4‐ethylenedioxythiophene)/polyvinylcarbazole (PVK)/70:30 (w/w) PFO–5PtTPP: 2‐(biphenyl‐4‐yl)‐5‐(4‐tert‐butylphenyl)‐1,3,4‐oxadiazole/Ba/Al device configuration. In comparison with the PFO–PtTPP copolymers synthesized via a postpolymerization metalation route, copolymerization from Pt metal complexes proved to be a more efficient synthetic route for high‐efficiency electrophosphorescent polymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4174–4186, 2006     

Water‐soluble conjugated polymers: Synthesis and optical properties

Two sets of water‐soluble poly(phenylene vinylene)s were synthesized and their optical properties were studied. The aqueous solubility of all these polymers is rendered by pendant sulfonate groups. One set of polymers (polymer I series) contains, in addition to the sulfonate pendants, dimethoxy substituents, while the other (polymer II series) contains oligo(ethylene oxide) side chains. Within each set, polymers containing lithium (Ia and IIa), sodium (Ib and IIb), and potassium (Ic and IIc) counter ions were prepared. The two sets of polymers showed different properties from physical appearance (fiber vs film) to thermal properties and to optical properties. It was found that set I polymers, with shorter side chains, exhibit stronger aggregation in aqueous solutions than set II polymers, which led to their lower fluorescence quantum yields and lower polymer‐to‐MV²⁺ quenching efficiencies. Within each set, the effect of counter ions on optical properties was noted. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5123–5135, 2007     

Synthesis and chiroptical properties of optically active photochromic methacrylic polymers bearing in the side chain the (S)-3-hydroxypyrrolidinyl group conjugated with the trans-azoaromatic chromophore

Novel optically active polymethacrylates, namely poly[(S)-3-methacryloyloxy-1-(4-azobenzene)pyrrolidine] and poly[(S)-3-methacryloyloxy-1-(4′-nitro-4-azobenzene)pyrrolidine], have been synthesized by radical polymerization of the corresponding monomers, prepared in turn through a synthetic route preserving the asymmetric center by any racemization reaction. These homopolymers are characterized by the presence in the side chain of an optically active pyrrolidinyl ring linked to the trans-azoaromatic system through the nitrogen atom. The optical activity of the polymers in solution appears much higher than that observed with the low molecular weight models, purposely synthesized for comparison. Circular dichroism spectra of the synthesized products demonstrated that, in solution, the macromolecules assume highly homogeneous conformations with a prevailing chirality to a larger extent with respect to analogous systems previously investigated. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3257–3268, 1999     

Ion‐Specific Self‐Assembly of Low‐Dimension Aggregate Structures of Conjugated Polymer at Two‐Phase Interface

A novel and facile approach to manipulate the morphology of Cu²⁺‐ion‐specific assembly of conjugated polymer by coordinative interaction at an oil–water two‐phase interface is present. The application of increasing importance is the use of π‐conjugated polymers as receptors, exploiting their ability to selectively form complexes, which can obviously change the optical properties in solution and induce the formation of varied solid nano/microstructures. By this method, microtubes are formed through self‐rolling of a strained ionic bilayer film at the oil/water interface.     

Synthesis of through‐space conjugated polymers containing [2.2]paracyclophane and thieno[3,4‐b]pyrazine in the main chain

We synthesized through‐space conjugated polymers with [2.2]paracyclophane and thieno[3,4‐b]pyrazine units in the main chain by the Sonogashira–Hagihara coupling reaction. The obtained polymers were soluble in common organic solvents, and homogeneous thin films were readily obtained from the polymer solutions by spin‐coating techniques. The polymers exhibited the extension of the conjugation length via the through‐space interaction. The polymers showed orangish‐red emission with peak maxima of around 610 nm in diluted solutions and their thin films, which were derived from the thieno[3,4‐b]pyrazine moieties. The optical and electrochemical behaviors of the polymers containing pseudo‐para‐ and pseudo‐ortho‐linked [2.2]paracyclophane were identical. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009