Synthesis and characterization of novel red‐emitting alternating copolymers based on fluorene and diketopyrrolopyrrole derivatives

Two novel alternating copolymers, poly{9,9‐dihexylfluorene‐2,7‐diyl‐alt‐2,5‐dioctyl‐3,6‐bis(4‐phenyl)pyrrolo[3,4‐c] pyrrole‐1,4‐dione} ( P1 ) and poly{9,9‐dihexylfluorene‐2,7‐diyl‐alt‐2,5‐dioctyl‐3,6‐bis(3‐phenyl)pyrrolo[3,4‐c] pyrrole‐1,4‐dione} ( P2 ), derived from 9,9‐dihexylfluorene and diketopyrrolopyrrole (DPP), have been successfully synthesized through palladium‐catalyzed Suzuki polycondensation in good yields. P1 and P2 possess moderate molecular weights and polydispersities, well‐defined structures, and excellent thermal properties with an onset decomposition temperature around 400 °C. Both P1 and P2 in thin films exhibit red photoluminescence from DPP species exclusively, with peaks at 609 and 616 nm, respectively. Cyclic voltammetry studies show that P1 and P2 have low‐lying lowest unoccupied molecular orbital energy levels at ?3.65 eV and reversible reduction processes, so these polymers may constitute another kind of red‐emitting polymer with high electron affinity. Preliminary electroluminescent results of devices with an indium tin oxide/poly(3,4‐ethylenedioxythiophene)/polymer/Ba/Al configuration reveal that P1 may be a promising candidate for red emitters with a maximum brightness of 153 cd/m² and a maximum external quantum efficiency of 0.13%, whereas the performance of P2 is relatively poor. These differences might originate from different conjugation lengths in their main chain. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2395–2405, 2006     

Synthesis and characterization of diphenylaminodiphenyl stryl based alternating copolymers

Diphenylaminobiphenylated stryl based alternating copolymers with phenyl or fluorene, which were expected to have a terphenylene vinylene backbone containing an (N,N‐diphenylamino)biphenyl pendant and a phenyl/fluorene/phenylene vinylene backbone containing an (N,N‐diphenylamino)biphenyl pendant, were synthesized by a Suzuki coupling reaction. The obtained copolymers were confirmed with various types of spectroscopy. The alternating copolymers showed good hole‐injection properties because of their low oxidation potential and good solubility and high thermal stability with a high glass‐transition temperature. The alternating copolymers showed blue emissions because of the adjusted conjugation lengths; the maximum wavelength was 460 nm for poly{4,4′‐biphenylene‐α‐[4″‐(N,N′‐diphenylamino)diphenyl]vinylene‐alt‐5‐(2′‐ethylhexyloxy)‐2‐methoxybenzene} and 487 nm for poly{4,4′‐biphenylene‐α‐[4″‐(N,N′‐diphenylamino)diphenyl] vinylene‐alt‐9,9‐dihexylfluorene}. The maximum brightness of indium tin oxide/poly(3,4‐ethylene dioxythiophene)/polymer/LiF/Al devices with poly{4,4′‐biphenylene‐α‐[4″‐(N,N′‐diphenylamino)diphenyl]vinylene‐alt‐5‐(2′‐ethylhexyloxy)‐2‐methoxybenzene} or poly{4,4′‐biphenylene‐α‐[4″‐(N,N′‐diphenylamino)diphenyl]vinylene‐alt‐9,9‐dihexylfluorene} as the emitting layer was 250 or 1000 cd/m², respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 341–347, 2007     

Silole‐containing poly(silylenevinylene)s: Synthesis,characterization, aggregation‐enhanced emission,and explosive detection

Hydrosilylation polymerizations of 1,1‐dimethyl‐2,5‐bis(4‐ethynylphenyl)‐3,4‐diphenylsilole with aromatic silylhydrides including 1,4‐bis(dimethylsilyl)benzene, 4,4′‐bis(dimethylsilyl)biphenyl, 2,5‐bis(dimethylsilyl)thiophene, and 2,7‐bis(dimethylsilyl)‐9,9‐dihexylfluorene in the presence of Rh(PPh₃)₃Cl catalyst in refluxed tetrahydrofuran afford a series of silole‐containing poly(silylenevinylene)s. Under optimum condition, the alkyne polyhydrosilylation reactions progress efficiently and regioselectively, yielding polymers with high molecular weights (M_w up to 95,300) and good stereoregularity (E content close to 99%) in high yields (up to 92%). The polymers are processable and thermally stable, with high decomposition temperatures in the range of 420?449 °C corresponding to 5% weight loss. They are weakly fluorescent in the solution state but become emissive in the aggregate and film states, demonstrating their aggregation‐enhanced emission characteristics. The explosive sensing capabilities of the polymers are examined in both solution and aggregate states. The emissions of the polymers aggregates in aqueous mixture are quenched more efficiently by picric acid in an exponential pattern with high quenching constants (up to 27,949 L mol^?1), suggesting that the polymers aggregates are sensitive chemosensors for explosive detection. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and fluorescent properties of conjugated copolymers containing maleimide and fluorene units at the main chain

Yamamoto or Suzuki–Miyaura coupling polymerizations of 2,3‐diiodo‐N‐cyclohexylmaleimide with fluorene derivatives (2,7‐dibromo‐9,9′‐dihexylfluorene and 9,9′‐dihexylfluorene‐2,7‐diboronic acid) were carried out. The number‐average molecular weights (M_n) of the resulting copolymers were 2600–3500 by gel permeation chromatography analysis. The fluorescence emission of the alternating copolymer showed the emission maxima at 551 nm in THF. On the other hand, the random copolymers showed the bimodal emission peaks at 418–420 and 555–557 nm region, respectively. The fluorescence peaks of the random copolymers on the long wavelength region (555–557 nm) were attributed to the conjugated neighboring N‐cyclohexylmaleimide‐9,9′‐dihexylfluorene units in the polymer main chain. Furthermore, the copolymers exhibited the fluorescence solvatochromism by the difference of the polarity of solvents. The alternating and random copolymers showed the different fluorescence solvatochromism, and the emission colors are distinguishable by the naked eye, respectively. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4945–4956     

Synthesis and chiroptical properties of chiral binaphthyl‐containing polyfluorene derivatives

New chiral binaphthyl‐containing polyfluorene (PF) derivatives, PFOH , PFMOM , and PFP , bearing different binaphthyl units ((S)‐2,2′‐bis(methoxymethoxy)‐1,1′‐binaphthyl for PFMOM , (S)‐1,1′‐binaphthyl‐2,2′‐diol for PFOH , and (S)‐2,2′‐bis(diphenylphosphinyl)‐1,1′‐binaphthyl for PFP ) in the backbone have been designed and synthesized through Pd‐catalyzed Suzuki polycondensation. Their properties have been investigated in detail by ¹H NMR, ¹³C NMR, TGA, DSC, UV–vis, photoluminescence (in solutions, in thin films before and after annealing), and circular dichroism (CD) spectroscopic methods compared with poly(9,9‐dihexylfluorene‐2,7‐diyl) ( PF ). The resulting copolymers possessed excellent solubility in organic solvents and emitted strong blue light. The phosphine oxide‐containing copolymers PFP and PFMOM exhibited higher quantum yields and better thermal spectral stability in comparison with PF . All the copolymers exhibited obviously the linearly polarized photoluminescent properties both in solutions and in solid states. High emission polarization ratios (R_PL) of PFP were observed with no obvious decrease upon thermal annealing. In addition, investigation of the CD spectroscopic properties of these copolymers in THF solutions indicated that the chirality of the binaphthyls could be transferred to the whole PF backbone. All these results demonstrated that introduction of the chiral binaphthyls, particularly BINAPO, into the backbone could effectively improve the performances of the copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Incorporation of fluorene‐based emitting polymers into silica

Novel polyfluorene copolymers with pendant hydroxyl groups, poly[2,7‐(9,9‐dihexylfluorene)‐2,7‐(9,9‐bis(6‐hydroxyhexyl)fluorene)‐co‐2,7‐(9,9‐dihexylfluorene)‐1,4‐phenylene] (PFP‐OH) and poly[2,7‐(9,9‐dihexylfluorene)‐2,7‐(9,9‐bis(6‐hydroxyhexyl)fluorene)‐co‐2,7‐(9,9‐dihexylfluorene)‐4,7‐(2,1,3‐benzothiadiazole)] (PFBT‐OH) were prepared. Acid‐catalyzed polycondensations of tetraethoxysilane were carried out in the presence of these polymers to obtain homogeneous hybrids. Photoluminescence spectra of these hybrids suggested the polymers were immobilized in silica matrix retaining their π‐conjugated structures. Further, hybrids of coat film were prepared utilizing perhydropolysilazane as a silica precursor. Their optical properties were examined. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis of new polyfluorene copolymers with a comonomer containing triphenylamine units and their applications in white‐light‐emitting diodes

Novel conjugated polyfluorene copolymers, poly[9,9‐dihexylfluorene‐2,7‐diyl‐co‐(2,5‐bis(4′‐diphenylaminostyryl)‐phenylene‐1,4‐diyl)]s (PGs), have been synthesized by nickel(0)‐mediated polymerization from 2,7‐dibromo‐9,9‐dihexylfluorene and 1,4′‐dibromo‐2,5‐bis(4‐diphenylaminostyryl)benzene with various molar ratios of the monomers. Because of the incorporation of triphenylamine (TPA) moieties, PGs exhibit much higher HOMO levels than the corresponding polyfluorene homopolymers and are able to facilitate hole injection into the polymer layer from the anode electrode in light‐emitting diodes. Conventional polymeric light‐emitting devices with the configuration ITO/PEDOT:PSS/polymer/Ca/Al have been fabricated. A light‐emitting device produced with one of the PG copolymers (PG10) as the emitting layer exhibited a voltage‐independent and stable bluish‐green emission with color coordinates of (0.22, 0.42) at 5 V. The maximum brightness and current efficiency of the PG10 device were 3370 cd/m² (at 9.6 V) and 0.6 cd/A, respectively. To realize a white polymeric light‐emitting diode, PG10 as the host material was blended with 1.0 wt % of a red‐light‐emitting polymer, poly[9,9‐dioctylfluorene‐2,7‐diyl‐alt‐2,5‐bis(2‐thienyl‐2‐cyanovinyl)‐1‐(2′‐ethylhexyloxy)‐4‐methoxybenzene‐5′,5′‐diyl] (PFR4‐S), and poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene] (MEH‐PPV). The device based on PG10:PFR4‐S showed an almost perfect pure white electroluminescence emission, with Commission Internationale de l'Eclairage (CIE) coordinates of (0.33, 0.36) at 8 V; for the PG10:MEH‐PPV device, the CIE coordinates at this voltage were (0.30, 0.40) with a maximum brightness of 1930 cd/m². Moreover, the white‐light emission from the PG10:PFR4‐S device was stable even at different driving voltages and had CIE coordinates of (0.34, 0.36) at 6 V and (0.31, 0.35) at 10 V. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1199–1209, 2007     

Optical and electronic properties of fluorene‐based copolymers and their sensory applications

A series of novel, fluorene‐based conjugated copolymers, poly[(9,9‐bis{propenyl}‐9H‐fluorene)‐co‐(9,9‐dihexyl‐9H‐fluorene)] ( P1 ), poly[(9,9‐bis{carboxymethylsulfonyl‐propyl}fluorenyl‐2,7‐diyl)‐co‐(9,9‐dihexyl‐9H‐fluorene)] ( P2 ) and poly[(9,9‐dihexylfluorene)‐co‐alt‐(9,9‐bis‐(6‐azidohexyl)fluorene)] ( P3 ), are synthesized by Suzuki coupling reactions and their electrochemical properties, in the form of films, are investigated using cyclic voltammetry. The results reveal that the polymer films exhibit electrochromic properties with a pseudo‐reversible redox behavior; transparent in the neutral state and dark violet in the oxidized state. Among the three polymers, P2 possesses the shortest response time and the highest coloration efficiency value. These polymers emit blue light with a band gap value of around 2.9 eV and have high fluorescent quantum yields. Their metal ion sensory abilities are also investigated by titrating them with a number of different transition metal ions; all of these polymers exhibit a higher selectivity toward Fe³⁺ ions than the other ions tested with Stern–Volmer constants of 4.41 × 10⁶M^?1, 3.28 × 10⁷M^?1, 1.25 × 10⁶M^?1, and 6.56 × 10⁶M^?1 for P1 , P2 , water soluble version of P2 ( P2S ) and P3 , respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Cationic,water‐soluble,fluorene‐containing poly(arylene ethynylene)s: Effects of water solubility on aggregation,photoluminescence efficiency,and amplified fluorescence quenching in aqueous solutions

Three novel fluorene‐containing poly(arylene ethynylene)s with amino‐functionalized side groups were synthesized through the Sonogashira reaction. They were poly{9,9‐bis[6′‐(N,N‐diethylamino)hexyl]‐2,7‐fluorenylene ethynylene}‐alt‐co‐{2,5‐bis[3′‐(N,N‐diethylamino)‐1′‐oxapropyl]‐1,4‐phenylene} ( P1 ), poly{9,9‐bis[6′‐(N,N‐diethylamino)hexyl]‐2,7‐fluorenylene ethynylene} ( P2 ), and poly({9,9‐bis[6′‐(N,N‐diethylamino)hexyl]‐2,7‐fluorenylene ethynylene}‐alt‐co‐(1,4‐phenylene)) ( P3 ). Through the postquaternization treatment of P1 – P3 with methyl iodide, we obtained their cationic water‐soluble conjugated polyelectrolytes (WSCPs): P1′ – P3′ . The water solubility was gradually improved from P3′ to P1′ with increasing contents of hydrophilic side chains. After examining the ultraviolet–visible absorption and photoluminescence (PL) spectra, fluorescence lifetimes, and dynamic light scattering data, we propose that with the reduction of the water solubility from P1′ to P3′ , they exhibited a gradually increased degree of aggregation in H₂O. The PL quantum yields of P1′ – P3′ in H₂O displayed a decreasing tendency consistent with the increased degree of aggregation, suggesting that the pronounced degree of aggregation was an important reason for the low PL quantum yields of WSCPs in H₂O. Two structurally analogous water‐soluble trimers of P2′ and P3′ , model compounds 2,7‐bis(9″,9″‐bis{6‴‐[(N,N‐diethyl)‐N‐methylammonium] hexyl}‐2″‐fluorenylethynyl)‐9,9‐bis{6′‐[(N,N‐diethyl)‐N‐methylammonium]hexyl}fluorene hexaiodide and 1,4‐bis(9′,9′‐bis{6″‐[(N,N‐diethyl)‐N‐methylammonium]hexyl}‐2′‐fluorenylethynyl)benzene tetraiodide, were synthesized. The amplified fluorescence quenching of these WSCPs by Fe(CN)₆⁴⁻ in H₂O was studied by comparison with a corresponding analogous trimer. The effects of aggregation on the fluorescence quenching may be two‐edged in these cases. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5778–5794, 2006     

Synthesis and characterization of white‐light‐emitting polyfluorenes containing orange phosphorescent moieties in the side chain

Two orange phosphorescent iridium complex monomers, 9‐hexyl‐9‐(iridium (III)bis(2‐(4′‐fluorophenyl)‐4‐phenylquinoline‐N,C^2′)(tetradecanedionate‐11,13))‐2,7‐dibromofluorene (Br‐PIr) and 9‐hexyl‐9‐(iridium(III)bis(2‐(4′‐fluorophenyl)‐4‐methylquinoline‐N,C^2′)(tetradecanedionate‐11,13))‐2,7‐dibromofluorene (Br‐MIr), were successfully synthesized. The Suzuki polycondensation of 2,7‐bis(trimethylene boronate)‐9,9‐dioctylfluorene with 2,7‐dibromo‐9,9‐dioctylfluorene and Br‐PIr or Br‐MIr afforded two series of copolymers, PIrPFs and MIrPFs, in good yields, in which the concentrations of the phosphorescent moieties were kept small (0.5–3 mol % feed ratio) to realize incomplete energy transfer. The photoluminescence (PL) of the copolymers showed blue‐ and orange‐emission peaks. A white‐light‐emitting diode with a configuration of indium tin oxide/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)/PIr05PF (0.5 mol % feed ratio of Br‐PIr)/Ca/Al exhibited a luminous efficiency of 4.49 cd/A and a power efficiency of 2.35 lm/W at 6.0 V with Commission Internationale de L'Eclairage (CIE) coordinates of (0.46, 0.33). The CIE coordinates were improved to (0.34, 0.33) when copolymer MIr10PF (1.0 mol % feed ratio of Br‐MIr) was employed as the white‐emissive layer. The strong orange emission in the electroluminescence spectra in comparison with PL for these kinds of polymers was attributed to the additional contribution of charge trapping in the phosphorescent dopants. © 2007 Wiley Periodicals, Inc. JPolym Sci Part A: Polym Chem 45: 1746–1757, 2007     

Bipyridinophane‐containing conjugated polymers modulated with an intramolecular aromatic C?H/π interaction

Bipyridinophane–fluorene conjugated copolymers have been synthesized via Suzuki and Heck coupling reactions from 5,8‐dibromo‐2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane and suitable fluorene precursors. Poly[2,7‐(9,9‐dihexylfluorene)‐co‐alt‐5,8‐(2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane)] ( P7 ) exhibits large absorption and emission redshifts of 20 and 34 nm, respectively, with respect to its planar reference polymer Poly[2,7‐(9,9‐dihexylfluorene)‐co‐alt‐1,4‐(2,5‐dimethylbenzene)] ( P11 ), which bears the same polymer backbone as P7 . These spectral shifts originate from intramolecular aromatic C? H/π interactions, which are evidenced by ultraviolet–visible and ¹H NMR spectra as well as X‐ray single‐crystal structural analysis. However, the effect of the intramolecular aromatic C? H/π interactions on the spectral shift in poly[9,9‐dihexylfluorene‐2,7‐yleneethynylene‐co‐alt‐5,8‐(2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane)] ( P10 ) is much weaker. Most interestingly, the quenching behaviors of these two conjugated polymers are largely dependent on the polymer backbone. For example, the fluorescence of P7 is efficiently quenched by Cu²⁺, Co²⁺, Ni²⁺, Zn²⁺, Mn²⁺, and Ag⁺ ions. In contrast, only Cu²⁺, Co²⁺, and Ni²⁺ ions can partially quench the fluorescence of P10 , but much less efficiently than the fluorescence of P7 . The static Stern–Volmer quenching constants of Cu²⁺, Co²⁺, and Ni²⁺ ions toward P7 are of the order of 10⁶ M^?1, being 1300, 2500, and 37,300 times larger than those of P10 , respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4154–4164, 2006     

Novel blue‐greenish electroluminescent poly(fluorenevinylene‐alt‐dibenzothiophenevinylene)s and their model compounds

Poly(9,9‐dihexylfluorene‐2,7‐vinylene‐alt‐dibenzothiophene‐2,8‐vinylene) (PS) and poly(9,9‐dihexylfluorene‐2,7‐vinylene‐alt‐dibenzothiophene‐5,5‐dioxide‐2,8‐ vinylene) (PSO) as well as corresponding model compounds were synthesized by Heck coupling. Both the polymers and model compounds were readily soluble in common organic solvents such as tetrahydrofuran, dichloromethane, chloroform, and toluene. The polymers showed a decomposition temperature at ～430 °C and a char yield of about 65% at 800 °C in N₂. The glass‐transition temperatures of the polymers were almost identical (75–77 °C) and higher than those of the model compounds (26–45 °C). All samples absorbed around 390 nm, and their optical band gaps were 2.69–2.85 eV. They behaved as blue‐greenish light emitting materials in both solutions and thin films, with photoluminescence emission maxima at 450–483 nm and photoluminescence quantum yields of 0.52–0.72 in solution. Organic light‐emitting diodes with an indium tin oxide/poly(ethylene dioxythiophene):poly(styrene sulfonic acid)/polymer/Mg:Ag/Ag configuration with polymers PS and PSO as emitting layers showed green electroluminescence with maxima at 530 and 540 nm, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6790–6800, 2006     

Synthesis and properties of fluorene or carbazole‐based alternating copolymers containing Si and vinylene units in the main chain

Alternating copolymerization of 9,9‐dihexyl‐2,7‐dibromofluorene (HFl), N‐hexyl‐2,7‐dibromocarbazole (2,7‐HCz) or N‐hexyl‐3,6‐dibromocarbazole (3,6‐HCz) with Si‐containing divinyl or diallyl compounds, divinyldimethylsilane, divinyldiphenylsilane, 1,3‐divinyltetramethyldisiloxane, 1,4‐bis(dimethylvinylsilyl)benznene, diallyldimethylsilane, or diallyldiphenylsilane has been investigated using Mizoroki‐Heck reaction with a Pd catalyst. The corresponding alternating copolymers were obtained in good yield. The alternating copolymers from HFl or 2,7‐HCz showed good solubility in typical organic solvents. On the other hand, the copolymer with 3,6‐HCz became insoluble due to the crosslinking. Photophysical properties of the resulting copolymers were investigated with UV–vis absorption and photoluminescence spectroscopy. All the copolymers showed absorption peak derived from π–π* transition at around 340 nm, which was blue shifted in comparison with that of the corresponding homopolymer. Whereas emission peaks of the copolymers of the cast film were red shifted in comparison with that of the homopolymers. Multiple broad absorption peaks, which would be derived from intramolecular charge transfer through σ–π moiety, were also detected in the range from 390 to 450 nm in the spectra of the copolymers containing Si‐vinylene unit. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4513–4521, 2008     

Arylamino‐functionalized fluorene‐ and carbazole‐based copolymers: Color‐tuning their CdTe nanocrystal composites from red to white

Four alternating arylamino‐functionalized copolymers were synthesized in a Suzuki copolymerization applying 4, 4′‐(2,7‐dibromo‐9H‐fluorene‐9,9‐diyl)dianiline, 4,4′‐(2,7‐dibromo‐9H‐fluorene‐9,9‐diyl)bis(N,N‐diphenylaniline), 4‐(3,6‐dibromo‐9H‐ carbazol‐9‐yl)aniline and 4‐(3,6‐dibromo‐9H‐carbazol‐9‐yl)‐N,N‐diphenylaniline in combination with 2,2′‐(9,9‐dioctyl‐9H‐fluorene‐2,7‐diyl)bis(1,3,2‐dioxaborinane). The resulting novel alternating copolymers were fully characterized. The copolymers revealed blue light emission and wide optical bandgaps of at least 2.93 eV for the fluorene‐based and 3.07 eV for the carbazole‐based polymers. The amino‐functions allow to tie semiconducting CdTe nanocrystals (NCs) and to synthesize a series of composites with CdTe NCs. Moreover, tuning the emission color over a wide range by tying these CdTe NCs results in a facile preparation of organic–inorganic semiconductor composites with emission colors “à la carte.” © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Donor–acceptor semiconducting polymers based on pyromellitic diimide

Three donor–acceptor copolymers P1 , P2 , and P3 with N,N′‐dodecylpyromellitic diimide as the electron‐acceptor unit with three diethynyl‐substituted donor monomers: 1,4‐diethynyl‐2,5‐bis(octyloxy)benzene, 2,7‐diethynyl‐9,9‐dioctyl‐9H‐fluorene, and 3,3′‐didodecyl‐5,5′‐diethynyl‐2,2′‐bithiophene have been synthesized by Sonogashira crosscoupling polymerization. The synthesized polymers showed deep highest occupied molecular orbital energy levels and larger band gaps (>2.5 eV). Polymers P1 , P2 , and P3 underwent fluorescence quenching with [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM), indicating the intermolecular photo‐induced charge transfer between the donor polymers and the PCBM acceptor. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1617–1622     

Phenothiazine‐S,S‐dioxide‐ and fluorene‐based light‐emitting polymers: Introduction of e−‐deficient S,S‐dioxide into e−‐rich phenothiazine

A novel series of poly(10‐hexyl‐phenothiazine‐S,S‐dioxide‐3,7‐diyl) and poly(9,9′‐dioctyl‐fluorene‐2,7‐diyl‐alt‐10‐hexyl‐3,7‐phenothiazine‐S,S‐dioxide) (PFPTZ‐SS) compounds were synthesized through Ni(0)‐mediated Yamamoto polymerization and Pd(II)‐catalyzed Suzuki polymerization. The synthesized polymers were characterized by ¹H NMR spectroscopy and elemental analysis and showed higher glass transition temperatures than that of pristine polyfluorene. In terms of photoluminescence (PL), the PFPTZ‐SS compounds were highly fluorescent with bright blue emissions in the solid state. Light‐emitting devices were fabricated with these polymers in an indium tin oxide/poly(3,4‐ethylene dioxythiophene):poly(styrene sulfonate)/polymer/Ca/Al configuration. The electroluminescence (EL) of the copolymers differed from the PL characteristics: the EL device exhibited a redshifted greenish‐blue emission in contrast to the blue emission observed in the PL. Additionally, this unique phenothiazine‐S,S‐dioxide property, triggered by the introduction of an electron‐deficient SO₂ unit into the electron‐rich phenothiazine, gave rise to improvements in the brightness, maximum luminescence intensity, and quantum efficiency of the EL devices fabricated with PFPTZ‐SS. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1236–1246, 2007     

Two‐photon excitation and optical limiting in polyfluorene derivatives

Fluorene‐based polymers are widely known materials due to a combination of features such as photoluminescence and electroluminescence, oxidative stability, and film‐forming ability. However, studies reporting nonlinear optical properties in this class of conjugated polymer are scarce. Here, we report a new class of polyfluorene derivatives poly(9,9′‐n‐dihexyl‐2,7‐fluorenedilvinylene‐alt‐1,4‐phenylenevinylene), poly(9,9′‐n‐dihexyl‐2,7‐fluorenedilvinylene‐alt‐2,5‐thiophene), and poly[(9,9‐di‐hexylfluorenediylvinylene‐alt‐1,4‐phenylenevinylene)‐co‐((9,9′‐(3‐t‐butylpropanoate) fluorene‐1,4‐phenylene)] displaying high two‐photon absorption (2PA) in the spectral range from a 490 to 1100 nm. The 2PA cross‐section peak values for these materials are as high as 3000 Göppert Mayer (1 GM = 1 × 10^?50 cm⁴ s/photon), which is related to the high degree of conjugation along the polymer backbone. The polymers that were used in this study presented a strong two‐photon luminescence and also displayed optical limiting behavior, which, in combination with their well‐established properties, make them highly suitable for nonlinear optical devices. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 50: 148–153, 2012     

Synthesis of cationic diacetylene‐co‐carbazole‐co‐fluorene polymers and their sensitive fluorescent quenching properties with DNA

Two neutral precursor conjugated copolymers based 2,7‐diethynylfluorene and 3,6‐diethynylcarbazole units in the main chain ( PFC and PF2C ) were prepared by Hay coupling polymerization. Their cationic copolymers ( CPFC and CPF2C ) were prepared by the methylation of their diethylpropylamino groups with CH₃I. For comparison, neutral conjugated homopolymers of 2,7‐diethynylfluorene ( PF ), 3,6‐diethynylcarbazole units ( PC ) and their cationic polymers ( CPF and CPC ) were also prepared with the same method. A comparative study on the optical properties of cationic polymers CPFC and CPF2C in DMF and DMF/H₂O showed that they underwent water‐induced aggregation. The spectral behaviors of CPFC and CPF2C with calf thymus DNA showed that a distinct fluorescent quenching took place with minute addition of CT DNA (3.3 × 10^?13 M). The results showed that the polymers would be promising biosensor materials for sensitive detection of DNA. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4168–4177, 2010     

Synthesis and properties of new fluorene‐based polyquinoxalines with an ether linkage in the main chain for light‐emitting diodes

A new series of fluorene‐based polyquinoxalines with an ether linkage in the main chain were prepared by the polycondensation reaction between a tetraketone monomer and 3,3′,4,4′‐tetraaminodiphenyl ether. The polycondensation was usually carried out in m‐cresol. The resulting polymers ( P1 – P3 ) [ P1 = poly(quinoxaline‐co‐9,9‐dihexyl‐2,7‐dimethyl‐9H‐fluorene) P2 = poly(quioxaline‐co‐9,9‐dihexyl‐9‐pentyl‐2,7‐di‐p‐tolyl‐9H‐fluorene) P3 = poly(quioxaline‐co‐9,9‐bis‐(4‐methoxy‐phenyl)‐2,7‐dimethyl‐9H‐fluorene)] showed good solubility in common organic solvents and high thermal stability with only a 5% weight loss up to 440 °C. P1 and P2 had very high glass‐transition temperatures of 212 and 223 °C, respectively, whereas P3 did not show any phase‐transition temperature in repeated scans up to 300 °C. All the polymers in photoluminescence showed blue emissions in the range of 432–465 nm, both in chloroform solutions and in thin films. Light‐emitting diode devices of the configuration indium tin oxide/poly(3,4‐ethylenedioxythiophene)/polymer:poly(N‐vinylcarbazole) blend (2:8)/LiF/Al were fabricated with P1 or P2 and emitted blue light with electroluminescence peak wavelengths of 434 and 448 nm, respectively. The maximum brightness and the external quantum efficiency of P1 were 0.56 μW/cm² at 29 V and 0.056%, whereas P2 showed 0.50 μW/cm² at 34 V and a relatively low value of 0.015%, respectively. Cyclic voltammetry studies revealed that these polymers possessed low‐lying ionization potential energy levels ranging from ?5.49 to ?5.86 eV and low‐lying electron affinity energy levels ranging from ?2.65 to ?2.88 eV. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1189–1198, 2006     

Synthesis and characterization of thiazolothiazole‐based polymers and their applications in polymer solar cells

A novel series of thiazolothiazole (Tz)‐based copolymers, poly[9,9‐didecylfluorene‐2,7‐diyl‐alt‐2,5‐bis‐(3‐hexylthiophene‐2‐yl)thiazolo[5,4‐d]thiazole] (P1), poly[9,9‐dioctyldibenzosilole‐2,7‐diyl‐alt‐2,5‐bis‐(3‐hexylthiophene‐2‐yl)thiazolo[5,4‐d]thiazole] (P2), and poly[4,4′‐bis(2‐ethylhexyl)‐dithieno[3,2‐b:2′,3′‐d]silole‐alt‐2,5‐bis‐(3‐hexylthiophene‐2‐yl)thiazolo[5,4‐d]thiazole] (P3), were synthesized for the use as donor materials in polymer solar cells (PSCs). The field‐effect carrier mobilities and the optical, electrochemical, and photovoltaic properties of the copolymers were investigated. The results suggest that the donor units in the copolymers significantly influenced the band gap, electronic energy levels, carrier mobilities, and photovoltaic properties of the copolymers. The band gaps of the copolymers were in the range of 1.80–2.14 eV. Under optimized conditions, the Tz‐based polymers showed power conversion efficiencies (PCEs) for the PSCs in the range of 2.23–2.75% under AM 1.5 illumination (100 mW/cm²). Among the three copolymers, P1, which contained a fluorene donor unit, showed a PCE of 2.75% with a short‐circuit current of 8.12 mA/cm², open circuit voltage of 0.86 V, and a fill factor (FF) of 0.39, under AM 1.5 illumination (100 mW/cm²). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011