Synthesis and luminescence properties of new blue‐light‐emitting polyconjugated poly{1,1′‐biphenyl‐4,4′‐diyl‐[1‐(4‐t‐butylphenyl)]vinylene} polymers and copolymers

Three new soluble polyconjugated polymers, all of which emitted blue light in photoluminescence and electroluminescence, were synthesized, and their luminescence properties were studied. The polymers were poly{1,1′‐biphenyl‐4,4′‐diyl‐[1‐(4‐t‐butylphenyl)]vinylene}, poly((9,9‐dioctylfluorene‐2,7‐diyl)‐alt‐{1,4‐phenylene‐[1‐(4‐t‐butylphenyl)vinylene‐1,4‐phenylene]}) [P(DOF‐PVP)], and poly([N‐(2‐ethyl) hexylcarbazole‐3,6‐diyl]‐alt‐{1,4‐phenylene‐[1‐(4‐t‐butylphenyl)]vinylene‐1,4‐phenylene}). The last two polymers had alternating sequences of the two structural units. Among the three polymers, P(DOF‐PVP) performed best in the light‐emitting diode devices of indium–tin oxide/poly(ethylenedioxythiophene) doped with poly(styrene sulfonate) (30 nm)/polymer (150 nm)/Li:Al (100 nm). This might have been correlated with the balance in and magnitude of the mobility of the charge carriers, that is, positive holes and electrons, and also the electronic structure, that is, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels, of the polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 307–317, 2006     

Synthesis and characterization of novel phenyl‐substituted poly(p‐phenylene vinylene) derivatives

Two novel phenyl‐substituted poly(p‐phenylene vinylene) derivatives, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylenevinylene} (EDP‐PPV) and poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDMP‐PPV), and their copolymer, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylene‐vinylene‐co‐2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDP‐co‐EDMP‐PPV; 4:1, 1:1, and 1:4), were successfully synthesized according to the Gilch route. The structures and properties of the monomers and the resulting conjugated polymers were characterized with ¹H‐NMR, ¹³C‐NMR, elemental analysis, gel permeation chromatography, thermogravimetric analysis, ultraviolet–visible absorption spectroscopy, and photoluminescence and electroluminescence (EL) spectroscopy. The EL polymers possessed excellent solubility in common solvents and good thermal stability with a 5% weight loss temperature of more than 380°C. The weight‐average molecular weights and polydispersity indices of EDP‐PPV, EDMP‐PPV, and EDP‐co‐EDMP‐PPV were 1.40–2.58 × 10⁵, and 1.19–1.52, respectively. Double‐layer light‐emitting diodes with the configuration of indium tin oxide/polymer/tris(8‐hydroxyquinoline)aluminum/Al devices were fabricated, and EDP‐co‐EDMP‐PPV (1:1) showed the highest EL performance and exhibited a maximum luminance of 1050 cd/m² at 19.5 V. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1259–1266, 2005     

Synthesis,characterization, and photophysical properties of novel poly(p‐phenylene vinylene) derivatives with conjugated thiophene as side chains

Two novel poly(p‐phenylene vinylene) (PPV) derivatives with conjugated thiophene side chains, P1 and P2, were synthesized by Wittig‐Horner reaction. The resulting polymers were characterized by ¹H‐NMR, FTIR, GPC, DSC, TGA, UV–Vis absorption spectroscopy and cyclic voltammetry (CV). The polymers exhibited good thermal stability and film‐forming ability. The absorption spectra of P1 and P2 showed broader absorption band from 300 to 580 nm compared with poly[(p‐phenylene vinylene)‐alt‐(2‐methoxy‐5‐octyloxy‐p‐phenylene vinylene)] (P3) without conjugated thiophene side chains. Cyclic voltammograms displayed that the bandgap was reduced effectively by attaching conjugated thiophene side chains. This kind of polymer appears to be interesting candidates for solar‐cell applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electroluminescence and photovoltaic properties of poly(p‐phenylene vinylene) derivatives with dendritic pendants

A copolymer of dendronized poly(p‐phenylene vinylene) (PPV), poly{2‐[3′,5′‐bis (2′‐ethylhexyloxy) bnenzyloxy]‐1,4‐phenylene vinylene}‐co‐poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylene vinylene] (BE‐co‐MEH–PPV), was synthesized with the Gilch route to improve the electroluminescence and photovoltaic properties of the dendronized PPV homopolymer. The polymer was characterized by ultraviolet–visible absorption spectroscopy, photoluminescence spectroscopy, and electrochemical cyclic voltammetry and compared with the homopolymers poly{2‐[3′, 5′‐bis(2‐ethylhexyloxy) benzyloxy‐1,4‐phenylene vinylene} (BE–PPV) and poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene] (MEH–PPV). Polymer light‐emitting diodes based on the polymers with the configuration of indium tin oxide (ITO)/poly(3,4‐ethylene dioxythiophene) : poly(styrene sulfonate) (PEDOT : PSS)/polymer/Ca/Al were fabricated. The electroluminescence efficiency of BE‐co‐MEH–PPV reached 1.64 cd/A, which was much higher than that of BE–PPV (0.68 cd/A) and a little higher than that of MEH–PPV (1.59 cd/A). Photovoltaic properties of the polymer were studied with the device configuration of ITO/PEDOT : PSS/polymer : [6,6J‐phenyl‐C₆₁‐butyric acid methyl ester] (PCBM)/Mg/Al. The power conversion efficiency of the device based on the blend of BE‐co‐MEH–PPV and PCBM with a weight ratio of 1 : 3 reached 1.41% under the illumination of air mass 1.5 (AM1.5) (80 mW/cm²), and this was an improvement in comparison with 0.24% for BE–PPV and 1.32% for MEH–PPV under the same experimental conditions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and Characterization of the Luminescent Poly[2-decyloxy-5-(2′,5′-bis(decyloxy)phenyl)-1,4-phenylenevinylene]

A new soluble luminescent poly[2-decyloxy-5-(2′,5′-bis(decyloxy)phenyl)-1,4-phenylenevinylene] (DBDP-PPV) is prepared by the dehydrohalogenation of 1,4-bis(bromomethyl)-2-decyloxy-5-(2′,5′-bis(decyloxy)phenyl) benzene (as monomer) in this study. The above monomer bearing decyloxy and 2′,5′-bis(decyloxy)phenyl substituents was prepared via such chemical reactions as alkylation, bromination, and Suzuki coupling reactions. The two asymmetric substituents on the phenylene ring make the DBDP-PPV soluble in organic solvents and eliminate the tolan-bis-benzyl (TBB) structure defects. The structure and properties of the DBDP-PPV are examined by ¹H-NMR, FT-IR, UV/Vis, TGA, photoluminescence (PL), and electroluminescence (EL) analyses. The DBDP-PPV film exhibits a PL peak at 519 nm. With the DBDP-PPV acting as a light-emitting polymer, a device is fabricated with a sequential lamination of ITO/PEDOT/DBDP-PPV/Ca/Ag. The EL spectrum of the device shows a maximum emission at 507 nm. The turn on voltage of the device is about 15.6 V. Its maximum brightness is 4.67 cd/m² at a voltage of 16.8 V.     

Synthesis and Characterization of New Cobalt(II)–Pyrazine Coordination Polymer as Precursor for Preparation of Co(II) Oxide Nanoparticles: Surprising Coordination,DFT Calculation and Spectroscopic Studies

The new 2-D cobalt(II) coordination polymer with pyrazine was synthesized surprisingly from reaction of CoCl₂ and tetrapyrido[3,2-a:2′,3′-c:3″,2″-h:2?,3?-j]phenazine (tpphz) in methanol as medium and characterized by means of Fourier transform infrared spectroscopy (FT-IR), UV–Vis spectroscopy and X-ray single crystal analysis. The results showed that coordination polymer consist of cobalt(II) chain with pyrazine-bridged which crystallizes in orthorhombic unit cell (a?=?10.1307, b?=?10.1310, c?=?10.6838 Å) and space group Pban. Density functional theory (DFT) calculations were also done to figure out the electronic structure of the compound from theoretical aspect. The electronic spectrum of coordination polymer was investigated and the DFT/TDDFT procedures were employed to assign the absorption bands. The thermal decomposition of the title compound resulted in formation of cobalt(II) oxide nanoparticles with average size of 50 nm.     

Synthesis of porphyrin-appended poly(fluorene-alt-carbazole): photoluminescent and electrochemical studies

Poly(fluorene-alt-carbazole) appended with meso-tetraphenylporphyrin (MTPPC) linked through oxyethylene spacer and the parent poly(N-hexyl-2,7-carbazole-alt-9,9-di-n-hexyl fluorene) (P1) were synthesized and characterized. Optical absorption properties of the polymers containing 5% of MTPPC (P2) and 10% of MTPPC (P3) in the polymer backbone show extended optical absorption toward long wavelength compared to the parent polymer P1. Optical absorption studies of the polymers showed that polymer P1 has absorption at 384 nm in solution, whereas polymers P2 and P3 have absorption at 384 nm corresponding to polymer backbone and soret band at 421 nm with Q bands at around 518 and 554 nm in solution. P1 shows photoluminescence emission around 417 nm, whereas P2 and P3 fall around 656 nm. Thermal, electrochemical, and quenching studies of the polymers have been studied and the details are reported.     

Synthesis and characterization of novel poly(arylenevinylene) derivative

The new poly(arylenevinylene) derivative composed naphthalene phenylene vinylene backbone was developed. The theoretical calculation showed that the model compound of the obtained polymer was highly distorted between the stryl and naphthalene units as well as between the backbone and fluorene side units. The polymer was synthesized by the palladium catalyzed Suzuki coupling reaction with 2,6‐(1′,2′‐ethylborate)‐1,5‐dihexyloxynaphtalene and 1,2‐bis(4′‐bromophenyl)‐1‐(9″,9″‐dihexyl‐3‐fluorenyl)ethene. The structure of the polymer was confirmed by ¹H NMR, IR, and elemental analysis. The weight–average molecular weight of the polymer is 29,800 with the polydispersity index of 1.87. The new polymer showed good thermal stability with high T_g of 195°C. The bright blue fluorescence (λ_max = 475 nm) was observed both in solution and film of new polymer with naphthalene phenylene vinylene backbone. Double layer LED devices with the configuration of ITO/PEDOT/polymer/LiF/Ca/Al showed a turn‐on voltage at around 4.5 V, the maximum luminance of 150 cd/m², and the maximum efficiency of 0.1 cd/A. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Emission properties of composite semiconducting polymer nanoparticles

A series of composite polymer nanoparticles was prepared from poly(N‐vinylcarbazole) (PVK) and poly(2,5‐bistriethoxy‐p‐phenylene vinylene‐alt‐phenylene vinylene) (BTEO–PPV‐alt‐PPV). The nanoparticle sizes were measured to be in the range of 50–80 nm with transmission electron microscopy. The photoluminescence intensity of PVK decreased with the content of BTEO–PPV‐alt‐PPV increasing in the composite polymer nanoparticles because the excited states in PVK were quenched by BTEO–PPV‐alt‐PPV. The emission from BTEO–PPV‐alt‐PPV was enhanced in the composite polymer nanoparticles because of energy transfer from PVK to BTEO–PPV‐alt‐PPV for excitation at the absorption maximum of PVK. The energy‐transfer efficiency was markedly improved in the composite polymer nanoparticles versus the composite polymer films according to emission spectral analyses. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Organosoluble and colorless fluorinated poly(ether imide)s derived from a highly contorted biphenyl-2,2′-diol bis(ether anhydride) and aromatic bis(ether amine)s with trifluoromethyl substituents

A series of new fluorinated aromatic poly(ether imide)s (PEIs) were prepared from highly contorted 2,2′-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride and various trifluoromethyl-containing bis(ether amine)s via chemical or thermal imidization. All the PEIs showed good solubility in a variety of organic solvents and could afford flexible, colorless, and transparent thin films via solution-casting. They showed cut-off wavelengths of Uv-vis absorptions below 380 nm and very low yellowness index (b* < 7.0). They also showed high thermal stability with the 10% weight loss temperature from 503 to 585 °C of in nitrogen or air atmosphere. The glass transition temperatures (T _gs) are recorded in the range of 194–254 °C by DSC. For a comparative study, another series of non-fluorinated PEIs derived from the same biphenyl-2,2′-diol bis(ether anhydride) with various bis(ether amine)s without the trifluoromethyl substituents were also synthesized and characterized.     

Crystallography and Structure–Property Relationships of 2,2″,4,4′,4″,6,6′,6″‐Octanitro‐1,1′ : 3′,1″‐Terphenyl (ONT)

An X‐ray crystallographic study of 2,2″,4,4′,4″,6,6′,6″‐octanitro‐1,1′ : 3′,1″‐terphenyl (ONT) has been carried out. The dihedral angles between benzene rings vary from 84.9° to 89.4°. Nonbinding interatomic distances of oxygen atoms inside all the nitro groups are shorter than the intermolecular contact radii for oxygen. On the basis of the DFT B3LYP/6‐31(d, p) method it was found that the difference between the X‐ray structure in the solid phase and DFT result for the gas phase is 98 kJ mol⁻¹, and the bearer of the highest initiation reactivity of the ONT molecule in the solid phase should be the nitro group at 4″‐position, in contrast to those at 4′‐ or 6′‐position that play this role in the isolated molecule. It has been stated that the nitro groups at the reaction centers of the ONT molecule are relatively well specified by their ¹⁵N NMR chemical shifts.     

Synthesis of conjugated polymers with broad absorption bands and photovoltaic properties as bulk heterojuction solar cells

Two new broad absorbing alternating copolymers, poly[1-(2,6-diisopropylphenyl)-2,5-bis(2-thienyl)pyrrole-alt-4,7-bis(3-octyl-2-thienyl)benzothiadiazole] (PTPTTBT-P1) and poly[1-(p-octylphenyl)-2,5-bis(2-thienyl)pyrrole-alt-4,7-bis(3-octyl-2-thienyl)benzothiadiazole] (PTPTTBT-P2), were prepared via Suzuki polycondensation with high yields. The two polymers were found to show characteristic absorption in the visible region of the solar spectrum. Interestingly the absorption of PTPTTBT-P1 was found to cover the visible region from 350 to 650 nm with the broad and flat absorption maximum from 440 to 510 nm in film and the absorption of PTPTTBT-P2 was found to cover the visible region from 350 to 950 nm with the relatively distinct absorption maxima at 425 and 522 nm and very weak absorption maximum at 832 nm in film. The electrochemical band gaps of the polymers were calculated to be 1.88 eV and 1.87 eV, respectively, while the optical band gaps of the polymers were calculated to be 1.94 eV and 1.87 eV, respectively. The photovoltaic properties of polymers were investigated with bulk heterojunction (BHJ) solar cells fabricated in ITO/PEDOT:PSS/polymer:PC₇₀BM(1:5 wt%)/TiOx/Al configurations. The maximum power conversion efficiency (PCE) of the solar cell composed of PTPTTBT-P1:PC₇₀BM as an active layer was 1.57% with current density (J_sc) of 8.17 mA/cm², open circuit voltage (V_oc) of 0.52 V and fill factor (FF) of 36%.     

Precursor routes to polyacetylene: The microstructure of the precursor polymers

In the synthesis of polyacetylene via precursor polymers it seems reasonable to assume that the morphology of the product will be dependent, at least to some extent, on that of the precursor. A full stereochemical analysis of precursor polymer structure requires the synthesis of a range of samples with different microstructures. Since this was not possible for the thermally unstable precursor polymers used for the synthesis of polyacetylene, we have conducted studies on the model system poly(7′,8′-bis(carboxymethyl)-bicyclo[2.2.2]octa-5′-ene-2′,3′-diyl)-1,2-ethenediyl. Infra-red and ¹³C n.m.r. studies establish that this thermally stable analogue of polyacetylene precursors can be prepared with a range of vinylene stereochemistries although it was not possible to establish the details of microstructure completely. Monomers for the synthesis of polyacetylene precursor polymers are potentially bidentate ligands and might be expected to show unusual behaviour with some classes of metathesis catalyst; however, the monomer for this model study showed a conventional response to a range of metathesis catalysts.     

Stille cross‐coupling applied to get higher molecular weight polymers: Synthesis,optoelectronic, Voc properties,and solar cell application

Conjugated polymers are highly desirable for the photovoltaic applications. We report the synthesis, characterization, optoelectronic properties, and solar cell application of two polymers, namely, poly[(9,9‐didodecylfluorene‐2,7‐diyl)‐alt‐(2,2′:5′,2″‐terthiophene‐5,5″‐diyl)] (P1) and poly[(1,4‐bis(dodecyloxy)benzene‐2,5‐diyl)‐alt‐(2,2′:5′,2″‐terthiophene‐5,5″‐diyl)] (P2). The polymers were synthesized via Stille cross‐coupling reaction, and were characterized by the gel permeation chromatography, nuclear magnetic resonance, Fourier transform infrared, UV–vis, thermogravimetric analysis, and cyclic voltammetry analyses. The two copolymers are processable due to their good solubility in organic solvents (tetrahydrofuran, CHCl₃, toluene, chlorobenzene, and o‐dichlorobenzene). The optical band gaps (UV–vis, film, and E_g^opt) of the P1 and P2 are 2.04 and 2.00 eV, respectively. The density functional theory output structures showed that S ^… O space interaction is likely responsible for the higher planarity of P2. The polymers showed low HOMO energy levels (P1: −5.33 eV, P2: −5.05 eV). The E_HOMO for P1 is close to the E_HOMO (−5.4 eV) of an ideal polymer, which is an important, rare, and main origin of the observed higher V_oc (801–808 mV). The onset decomposition temperatures (T_d) for the P1 and P2 are 418°C and 365°C, respectively. The polymer solar cell based on the P1: C₆₀ (1: 1) and P2: C₆₀ (1: 1) blend showed a power conversion efficiency (PCE) of 0.94 and 0.71%, respectively. The composite polymer : PC₆₀BM = 1 : 2 increased PCE of the P1 (1.65%) and P2 (1.09%) under AM 1.5 illumination (100 mW/cm²). The study provided important examples to design donor–donor (D–D) polymers for the photovoltaic applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42147.     

Synthesis of oxadiazole‐based polymers containing a carbazole–vinylene or fluorene–vinylene group and their hole‐injection/transport behavior in light‐emitting diodes

A series of conjugated (poly{N‐(2‐ethylhexyl)‐3,6‐carbazole–vinylene‐alt‐[(2,5‐bisphenyl)‐1,3,4‐oxadiazole]}) and nonconjugated (poly{N‐(2‐ethylhexyl)‐3,6‐carbazole–vinylene‐alt‐[(2,5‐bisphenol)‐1,3,4‐oxadiazole]}) and poly{9,9‐dihexyl‐2,7‐fluorene–vinylene‐alt‐[(2,5‐bisphenol)‐1,3,4‐oxadiazole]}) polymers containing oxadiazole and carbazole or fluorene moieties in the polymer backbone were synthesized with a multiple‐step procedure. The properties of the polymers, including the photophysical and electrochemical characteristics, could be fine‐tuned by adjustment of the components or structures in the polymer chains. The polymers were used to examine the hole‐injection/transport behavior as hole‐injection/hole‐transport layers in double‐layer indium tin oxide (ITO)/polymer/aluminum tris(8‐hydroxyquinoline)/LiF/Al devices by the determination of their energy levels. The effects of the polymers in these devices on the charge‐transport behavior were compared with a control device fabricated with poly(ethylenedioxythiophene) (PEDOT)–poly(styrene sulfonate) (PSS). Devices containing the synthesized polymers showed comparable adhesion to the ITO anode and good hole‐injection/transport performance. In addition, they exhibited higher electroluminescence over an identical range of current densities than the control device. This was attributed to the prevention of radiative exciton quenching caused by the PEDOT–PSS interfaces and the improvement of electron/exciton blocking due to the higher electron affinity of the synthesized polymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Luminescent supramolecular polymers: Cd2+‐directed polymerization and properties

A family of supramolecular polymers was prepared via Cd²⁺‐directed self‐assembly polymerization of bis(2,2′:6′,2″‐terpyridine)‐based ligand monomers, using oligofluorenes and triphenylamine as bridges under mild conditions. The polymers were fully characterized using thermogravimetric analysis, inherent viscosity, electrochemical measurements, UV‐visible spectroscopy, photoluminescence (PL) and electroluminescence (EL). Polymers with oligofluorenes as spacers exhibited blue emission (434–442 nm) in dimethyl acetamide (DMAc) solution, while polymers with triphenylamine as spacer presented an emission peak at 494 nm in DMAc solution. Complexation polymerization of bis(2,2′:6′,2″‐terpyridine)‐based ligand monomers with cadmium(II) improved fluorescence quantum yields dramatically, and the film PL quantum yields of these polymers were about 0.38–0.54. Single‐layer light‐emitting diodes were fabricated with the configuration indium tin oxide (ITO)/polymer/Ca/Al; the EL showed green emission and the onset voltages of the devices were 8–11 V. Copyright © 2006 Society of Chemical Industry     

Acidic ionic liquid polymers: <Emphasis Type="Italic">poly</Emphasis>(<Emphasis Type="Italic">bis</Emphasis>-imidazolium-<Emphasis Type="Italic">p</Emphasis>-phenylenesulfonic acid) and applications as catalysts in the preparation of 1-amidoalkyl-2-naphthols

A new class of polymeric acidic ionic liquids with imidazolium hydrogen sulfate and p-phenylene sulfonic acid units built into the main polymer chain were prepared by a simple two step method in 87–89% yield. These new polymers were characterized by elemental analysis, ¹H, ¹³C NMR, FT-IR, TGA and GPC. The catalytic activity of sulfonic acid group functionalized ionic liquid polymers was demonstrated through the synthesis of 1-amidoalkyl-2-naphthols in 78–90% yield by condensation of 2-naphthol, benzaldehyde and amides without a solvent at 100 °C.     

Optimization of controlled ring-opening polymerization of <Emphasis Type="SmallCaps">l</Emphasis>-lactide to hydroxyl terminated polylactides using zinc acetate catalyst

Hydroxyl terminated polylactide polymers with number of average molecular weights (M _n ) varying from 1625 to 3459 g mol^?1 were synthesized by ring opening bulk polymerization of lactide in the presence of zinc acetate being a potent catalyst. The use of 1,4 butanediol (BDO) initiator leads to hydroxyl terminated polylactides, thus excellent precursors for shape-memory biodegradable polyurethanes. Different reaction conditions employed for the synthesis of hydroxyl terminated polylactide polymers via activated monomer mechanism may result in differences in M _n , percentage mass conversion and percentage degree of crystallinity (%χ _c ) of the product. Influence of process parameters, i.e. catalyst concentration, initiator concentration, reaction temperature and time on characteristics of hydroxyl terminated polylactides was studied. These polymers were characterized by Nuclear Magnetic Resonance (¹H-NMR) spectroscopy, Fourier transforms infrared (FTIR) spectroscopy, gel permeation chromatography (GPC) and X-ray diffraction (XRD) techniques. FTIR and ¹H-NMR confirmed the formation of hydroxyl terminated polylactides. M _n was determined by ¹H-NMR, GPC and end group analysis. %χ _c was calculated from XRD spectra. Maximum mass conversion, M _n and %χ _c were observed at 5 mol% SnOct₂ and 5 mol% BDO concentration. At optimum temperature of 145 °C, these characteristics improved linearly with polymerization time up to 6 h and declined thereafter.     

Syntheses and optical,electrochemical, and photovoltaic properties of polymers with 6-(2-thienyl)-4H-thieno[2,3-b]indole with a variety of electron-deficient units

Conjugated polymers were synthesized and used for polymer solar cells with new electron-rich units, 6-(2-thienyl)-4H-thieno[2,3-b]indole (2-TTI). 2-TTI was coupled with electron-pulling units, including benzothiadiazole and benzimidazole derivatives, to provide push–pull types of conjugated polymers (poly(8-(heptadecan-9-yl)-6-(thiophen-2-yl)-8H-thieno[2,3-b]indole)-alt-(2-methyl-5,6-bis(octyloxy)-4,7-di(thiophen-2-yl)-2-(trifluoromethyl)-2H-benzimidazole) (PTTIDOCF3), poly(8-(heptadecan-9-yl)-6-(thiophen-2-yl)-8H-thieno[2,3-b]indole)-alt-(5,6-bis(octyloxy)-4,7-di(thiophen-2-yl)-2,1,3-benzothiadiazole) (PTTIDOBT), poly(8-(heptadecan-9-yl)-6-(thiophen-2-yl)-8H-thieno[2,3-b]indole)-alt-(2,2-dimethyl-4,7-di(thiophen-2-yl)-2H-benzimidazole) (PTTIMBI), and poly(8-(heptadecan-9-yl)-6-(thiophen-2-yl)-8H-thieno[2,3-b]indole)-alt-(2,2-dimethyl-5,6-bis(octyloxy)-4,7-di(thiophen-2-yl)-2H-benzimidazole) (PTTIDOMBI)). The synthesized conjugated polymers provided deep highest occupied molecular orbital energy levels for higher open-circuit voltages (V_OC). The device composed of PTTIDOMBI and [6,6]-Phenyl C₇₁ butyric acid methyl ester PC₇₁BM (1:2) with chloronaphthalene additive showed a V_OC of 0.72 V, a short-circuit current (J_SC) of 9.16 mA/cm², and a fill factor of 0.43; this gave a power conversion efficiency (PCE) of 2.84%. The PTTIDOMBI provided better morphology for enhanced charge transport, and this led to the higher J_SC and PCE of the organic solar cells. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47624.     

Synthesis and characterization of highly fluorescent phenylene vinylene containing perfluorocyclobutyl (PFCB) aromatic ether polymers

4-(Trifluorovinyloxy)benzaldehyde was treated under Wittig conditions with 4-dihexyloxy-2,5-xylenebis(triphenylphosphoniumbromide) to form 1,4-bis(2′-(4-trifluorovinyloxyphenyl)ethenyl)-2,5-dihexyloxybenzene, a novel phenylene vinylene-bistrifluorovinyl ether monomer. Cyclopolymerization afforded an insoluble, non-luminescent material likely due to cross-addition reactions between phenylene vinylene olefin and trifluorovinyl ether (TFVE). However, 1,2-bis(4-formylphenoxy)hexafluorocyclobutane was polymerized with 1,4-dihexyloxy-2,5-xylenebis(triphenylphosphoniumbromide) and 1-methoxy-4-(2-ethylhexyloxy)-2,5-xylenebis(triphenylphosphoniumbromide) under Wittig conditions to yield two novel poly(perfluorocyclobutyl-co-phenylene vinylene) polymers. The polymers are of moderate molecular weight (8600-8700 M_n), show excellent thermal stability (T_d = 390-405 °C), and are readily soluble in common organic solvents. The materials are highly fluorescent in both solution and thin film with solution quantum yields of 68 and 71%.