Synthesis of highly conjugated poly(3,9-carbazolyleneethynylenearylene)s emitting variously colored fluorescence

Novel conjugated polymers P1–P7 containing 3,9-linked carbazole units in the main chain were synthesized by the polycondensation of 3-ethynyl-9-(4-ethynylphenyl)carbazole (EEPCz) and dihaloarenes, and their optical and electrical properties were studied. Polymers with weight-average molecular weights of 4100–48,000 were obtained in 24–92% yields by the Sonogashira coupling polycondensation in tetrahydrofuran (THF)/Et₃N at 30 or 50 °C for 48 h. All the polymers absorbed light around 350 nm. The polymers with electron-accepter units exhibited absorption bands originating from charge transfer. The polymers except the one containing azobenzenes emitted variously colored fluorescence with moderate quantum yields upon excitation at the absorption maxima. P1–P3 were oxidized around 0.6 V, and then reduced around 0.5 V. The conductivity of P3 was 1.1 × 10⁻¹⁴ S/cm at 10³ V/cm.     

Synthesis of poly(p-phenylene vinylene) and derivatives via a new precursor route, the dithiocarbamate route

A new synthetic route towards poly(para-phenylene vinylene) (PPV) and its derivatives has been investigated. In this route, a bis-dithiocarbamate monomer is polymerized towards a dithiocarbamate precursor polymer by the addition of a strong base (LDA). The corresponding conjugated polymer is obtained via a heat treatment of the precursor polymer. This dithiocarbamate (DTC) precursor route strikes an optimal balance between several straightforward but sometimes troublesome precursor routes and the more complex sulphinyl precursor route yielding superior purity materials. The novelty lies in the fact that the monomer synthesis is not as difficult as compared to the sulphinyl route and this without losing the quality and accessibility of the precursor polymer. In the paper, the mechanism of the polymerization process is discussed and strong indications for radical as well as anionic mechanisms are presented.     

Optical, electrochemical and electrogravimetric behavior of poly(1-methoxy-4-(2-ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV) films

Poly(1-methoxy-4-(2-ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV) films spin-cast from chloroform solution were characterized by cyclic voltammetry, in situ spectroelectrochemistry, and electrochemical quartz crystal microbalance (EQCM) measurements. The MEH-PPV films exhibited two well-defined redox waves during p- and n-electrochemical doping, and a mass gain at the end of each cycle that is characteristic of the movement of ions and solvent into and out the film. The electronic energy gap of MEH-PPV was estimated as 2.35 eV from the anodic and cathodic onset potentials obtained by cyclic voltammetry, in good agreement with the value of optical energy gap determined from the absorption edge, 2.21 eV. The films also showed a reversible and stable electrochromic transition at a positive range of applied potentials from reddish-orange (neutral form) to brownish-green (oxidized form).     

Synthesis and gas permeability of ester substituted poly(p-phenylene)s

Polymerizations of various ester substituted 2,5-dichlorobenzoates [substituent: linear alkyl groups (1a-f), branched alkyl groups (1g-l), cyclohexyl groups (1m-o), phenyl groups (1p-r), and oxyethylene units (1s-v)] were investigated with Ni-catalyzed/Zn-mediated system in 1-methyl-2-pyrrolidone (NMP) at 80 °C. Most of monomers bearing linear and branched alkyl groups successfully polymerized to give relatively high-molecular-weight polymers (M_n = 10,000-20,800). However, the molecular weight of the polymer having eicocyl groups was low because of steric hindrance of long alkyl chain. The polymerizations of cyclohexyl 2,5-dichlorobenzoate and phenyl 2,5-dichlorobenzoate produced low-molecular-weight polymers, while the polymerizations of monomers with alkyl cyclohexyl and alkyl phenyl groups proceeded to afford polymers with relatively high-molecular-weights. The polymers possessing oxyethylene units were obtained, but the molecular weights were low when the oxyethylene chains were long. The gas permeability of membranes of poly(p-phenylene)s with alkyl chains increased as increasing the length of alkyl chain. The membranes of poly(p-phenylene)s with phenyl groups and oxyethylene units exhibited high densities and relatively low gas permeability. However, the CO₂/N₂ separation factor of membrane of poly(p-phenylene) having oxyethylene units was as large as 73.6.     

An effect of side chain length on the solution structure of poly(9,9-dialkylfluorene)s in toluene

The effect of side chain length of π-conjugated poly(9,9-dialkylfluorene)s has been studied in semi-dilute (10 mg/mL) toluene solutions using small-angle neutron scattering (SANS) and ¹H and ²H NMR spectroscopies. Under these conditions, SANS data indicate that poly(9,9-dinonylfluorene) and poly(9,9-dioctylfluorene) are dissolved down to the molecule level and appear as elongated one-dimensional chains (length >20-30 nm). In contrast, the shorter side chain polymers exhibit a self-association so that poly(9,9-diheptylfluorene) forms thin sheet-like (∼1 nm) and poly(9,9-dihexylfluorene) thin (∼1 nm) and thick sheet-like (>6 nm) aggregates. ¹H NMR data, together with the density functional theory (DFT) calculations, however, show that this occurs without changes in the conformation of the polymer backbone.     

Geometrical structures of poly(haloalkyl propiolate)s prepared with a [Rh(norbornadiene)Cl]2 catalyst

The polymerization of ω-haloalkyl propiolates initiated by [Rh(norbornadiene)Cl]₂ in methanol has been investigated in detail together with the geometrical forms of the resulting polymers. The polymer yield and molecular weight of poly(2-haloethyl propiolate)s (P(2XEPA)s) were markedly reduced in the order of X = Cl, Br, and I. ¹H NMR, electron spin resonance, and diffuse reflective UV-vis spectroscopic studies of P(2XEPA)s revealed that the content of cis form regarding the CC was markedly decreased from 60% for P(2ClEPA) to 15% for P(2IEPA). The decrease in the cis content also resulted in notable reduction of the crystallinity of the polymer from 30% for P(2ClEPA) to less than 10% for P(2IEPA). Compression of P(2XEPA)s at room temperature induced the so-called cis-to-trans isomerization accompanied with decomposition of the polymers.     

Branched poly(p‐phenylenevinylene): Synthesis,optical and electrochemical properties

A series of poly(p‐phenylene vinylene) (PPV) derivatives with phenylene vinylene side chains (branched PPVs), PPV0, PPV1, PPV2, and PPV3, were synthesized by the Heck coupling reaction and characterized by TGA, absorption spectra, photoluminescence (PL) spectra, and electrochemical cyclic voltammetry. The branched PPVs showed two absorption peaks in the UV–vis region, corresponding to the conjugated side chains (UV absorption) and the main chains (the visible absorption). Especially the absorption spectrum of PPV3 covers a broad wavelength range from 300 to 500 nm. Introducing the electron‐donating alkoxy substituents on the PPV main chains and increasing the content of the alkoxy groups lead to bathochromic shift of both absorption and PL spectra from PPV1 to PPV2 to PPV3. The onset oxidation potential of the branched PPVs is lower by 0.1–0.2 V than that of PPV, indicating that the electron‐donating ability of the branched PPVs enhanced in comparison with that of PPV. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Poly(dibenzo[a,c]phenazine-2,7-diyl)s - Synthesis and characterisation of a new family of electron-accepting conjugated polymers

A new family of conjugated polymers containing dibenzo[a,c]phenazine moieties, and hence having moderately high electron affinities, has been synthesized. Syntheses were achieved using Yamamoto or Suzuki couplings with 2,7-dibromodibenzo[a,c]phenazine derivatives as monomers. Several of the polymers had significant molecular weights and were still soluble in tetrahydrofuran or chloroform. A series of model compounds were also synthesized to assist in characterizing the polymers. The UV-vis spectra of the various materials gave clear evidence of the existence of conjugation along the polymer backbones. Fluorescence measurements indicate that emission in the green to orange region, and possibly beyond, is sensitive to the 11- and 12-substituents on the dibenzophenazine moieties. Finally, cyclic voltammetry demonstrates the electron-accepting nature of these materials with electron affinities in the range 2.6-3.2 eV.     

Synthesis of hydroxyphenylglycine-derived novel poly(silylenevinylenephenyleneethynylene)s

The hydrosilylation polymerization of d-(−)-p-hydroxyphenylglycine-derived diethynyl monomers 1p and 1m with dihydrosilanes Si1 and Si2 was carried out using RhI(PPh₃)₃ as a catalyst to give optically active novel poly(silylenevinylenephenyleneethynylene)s [(E)-poly(1p-Si1), (E)-poly(1p-Si2), (E)-poly(1m-Si1), (E)-poly(1m-Si2), and (Z)-poly(1p-Si1)] with number-average molecular weights ranging from 2800 to 17,000 in 41-92% yields. Polymers having (E)- and (Z)-olefin moieties were obtained, wherein the (E)-/(Z)-ratios depended on the reaction conditions. The UV-vis absorption edge of (E)-poly(1p-Si1) was positioned at a wavelength longer than that of (Z)-poly(1p-Si1), indicating that (E)-vinylene-linkage extends the conjugation more largely than the (Z)-counterpart. This was also confirmed by fluorescence spectroscopy. Alkaline hydrolysis of ester moieties of these polymers gave the corresponding polymers having carboxy groups. The (E)-polymers showed different solubility in hydrophobic solvents before and after hydrolysis, but the non-hydrolyzed and hydrolyzed (Z)-polymers exhibited the same solubility.     

Water-soluble conjugated polyelectrolyte with pendant glycocluster: Synthesis and its interaction with heparin

A novel fluorescent conjugated polyelectrolyte with pendant glucosamine hydrochloride clusters was prepared through Cu(I)-catalyzed azide/alkyne “click” ligation and Suzuki coupling polymerization. Compared with monosugar-functionalized conjugated polymer, the water-solubility and fluorescence quantum yield of the glycocluster-containing polymer (P-3) were significantly improved. As a glucosamine-containing cationic fluorescent polyelectrolyte, the water-soluble fluorescent polymer can interact with heparin through electrostatic bindings, which induce great fluorescence quenching of P-3 due to the polymer aggregation. Furthermore, upon treatment of the P-3-heparin ensemble with protamine, the fluorescence emission of P-3 recovered since the protamine possesses a competitively strong binding affinity to the heparin and thus results in the release of the fluorescent glycopolymer P-3 from the P-3-heparin ensemble.     

Synthesis and property studies of linear and kinked poly(pyreneethynylene)s

A series of fluorescent conjugated polymers, poly(pyreneethynylene)s, have been designed and synthesized to investigate the effect of shape of polymer backbone on physical properties. Polymers with linear and kinked backbone were synthesized using 1,6- and 1,8-disubstituted pyrene. The target copolymers were designed to incorporate various spacer units, such as, alkoxyphenyl, carbazole and fluorene on the polymer backbone. Characterization of the target compounds was achieved by NMR, IR, GPC and MALDI-TOF mass spectrometry. Detailed investigation on their optical, electrochemical and thermal properties revealed significant contribution of the geometry of polymer backbone towards physical properties. Kinked backbone of cisoid-polymers was found to result in lower optical band gap, less negative E_HOMO and higher thermal stability as compared to their linear analogues, most probably due to the coiling of polymer chains. Comparison of the physical properties of the polymers with those of the model compounds suggested similar extent of conjugation through 1,6- and 1,8-position of pyrene.     

Polymer conformation-assisted wrapping of single-walled carbon nanotube: The impact of cis-vinylene linkage

A soluble π-conjugated polymer cis-PmPV is found to be twice as effective as its trans-PmPV isomer in dispersing SWNTs into organic solvents. The improved efficiency is related to the specific conformation of cis-vinylene-enriched PmPV, which facilitates a planar π-π interaction with SWNT surface and leads to improved nanotube dispersion. ¹H NMR spectra indicate that the cis-CHCH bonds are partially converted to the trans-CHCH, thereby providing necessary conformational cavity for SWNT wrapping. Irradiation triggers a precipitation from SWNT dispersion, providing a purified SWNT/conjugated polymer composite.     

Synthesis and properties of sulfonated poly(2,5-diphenethoxy-p-phenylene)

A novel regio-controlled poly(2,5-diphenethoxy-p-phenylene) partially functionalized with sulfonic acids has been developed for a proton exchange membrane. Poly(2,5-diphenethoxy-p-phenylene) was prepared via the oxidative-coupling polycondensation using iron(III) trichloride as an oxidant. A high molecular weight polymer over 270,000 in the weight-average molecular weight was quantitatively obtained in mild conditions. This polymer was then reacted with two and four equimolar trimethylsilylchlorosulfonate in dichloromethane to give the corresponding sulfonic acid-functionalized polymers, whose functionalities were 0.69 and 1.19 per a polymer unit, which were translated to be 1.73 and 2.49 mequiv/g in ion exchange capacity (IEC), respectively. These polymers showed excellent proton conductivity up to 2 × 10⁻¹ S/cm at 80 °C and 95% relative humidity.     

Triphenylamine-based fluorescent conjugated glycopolymers: Synthesis, characterization and interactions with lectins

Two well-defined triphenylamine-based fluorescent conjugated glycopolymers were easily synthesized through Suzuki coupling polymerization of peracetylated galactopyranosyl-carrying monomer and consequent efficient deacetylation under Zemplén condition. Their structures were characterized using ¹H NMR, IR, and UV-vis spectroscopies. The preliminary insight into carbohydrate-lectin interactions was revealed by the titration of peanut agglutinin (PNA) to one of the final polymers, d-galactose-bearing poly(fluorene-alt-triphenylamine) copolymer (P-2), resulting in a significant fluorescence quenching of the polymer with a Stern-Volmer quenching constant of 1.56 × 10⁵ M⁻¹. Whereas no distinct change in the fluorescent properties of P-2 was observed when concanavalin A (Con A) was employed.     

Benzocyclobutene-functionalized poly(m-phenylene): A novel polymer with low dielectric constant and high thermostability

A novel benzocyclobutene-functionalized poly(m-phenylene) was synthesized. This polymer showed good solubility and film-forming ability. When being heated at high temperature, the polymer film converted to an insoluble cross-linked network structure and did not show any cracks. Thermogravimetric analysis of the polymer film exhibited a weight loss of 5% at 547 °C and a char yield of 71% at 1000 °C in nitrogen. Moreover, the cured film had good dielectric and mechanical properties. In a range of frequencies from 0.10 MHz to 30 MHz, the cured film showed dielectric constant of less than 2.7, which was comparable with these of polyimides, polycyanates and the SILK resins. On a nano indenter system, the cured film showed an average hardness of 1.05 GPa and a Yong's modulus of 39.18 GPa. Those data imply that the polymer could be used as the varnish for enameled wire, sizing agents for high performance carbon-fiber, and encapsulation resins in microelectronic industry.     

Thiophene-containing poly(arylene-ethynylene)-alt-poly(arylene-vinylene)s: Synthesis, characterisation and optical properties

This work describes the synthesis and characterisation of two types of thiophene-containing poly(arylene-ethynylene)-alt-poly(arylene-vinylene)s (PAE-PAV) copolymers, whose repeating units (-Ph-CC-Th-CHCH-Ph-CHCH-)_n, 5, and (-Th-CC-Ph-CC-Th-CHCH-Ph-CHCH-)_n, 8a-c, consist, respectively, of a 1:2 and a 2:2 ratio of triple bond/double bond moieties. Comparison of their photophysical, electrochemical and photovoltaic properties has been carried out. Although similar electrochemical data (HOMO: −5.43 eV, LUMO: ∼−3.15 eV, ) as well as identical thin film absorption behaviour (λ_a=500 nm, ) were obtained for both types of materials, significant differences in their thin film photoluminescence behaviour and photovoltaic properties were observed. While polymer 5 shows a fluorescence maximum at λ_e=568 nm (with a fluorescence quantum yield of Φ_f=7%), a total fluorescence quenching was observed in 8. Far better photovoltaic performance was obtained from solar cells (set up: ITO/PEDOT:PSS/active layer/LiF/Al; active layer consisting of 5 or 8b as donor and PCBM as acceptor in a 1:3 ratio by weight) designed from 5 than from 8b. Open circuit voltage, V_OC, as high as 900 mV and power conversion efficiency, η_AM1.5, around 1.2% were obtained. This can be attributed to the 1:2 triple bond/double bond ratio as well as the grafting of shorter octyloxy and 2-ethylhexyloxy side chains in 5 and to its comparatively higher molecular-weight.     

Synthesis and characterization of soluble poly(N-heptyl indole)

In view of preparing soluble polyindole, indole was N-alkylated using bromoheptane and polymerized to poly(N-heptyl indole) which is soluble in common organic solvents. This process is being reported for the first time. Poly(N-heptyl indole) was characterized by spectral, thermal methods and it shows photoluminescence in liquid state.     

Synthesis and characterization of hyperbranched poly(ester-amine) by Michael addition polymerization

A series of tertiary amine-based hyperbranched poly(amine-ester)s have been synthesized by Michael addition polymerization of trifunctional monomer, TMEA and difunctional monomer, diacylates in chloroform, and the resultant polymers were subsequently treated with mercaptoethenol or 1-dodecanethiol for improving stability in storage. The caption efficiency of mercaptoethanol is much better than that of 1-dodecanthiol. Kinetic study reveals that the thiol group is consumed faster than the acrylate group when the polymerization with feed molar ratio of diacrylate/TMEA = 2/1 was carried out. At initial polymerization, monomer conversion increases fast, but the molecular weights increase slowly and sharp increase of the molecular weight occurs at the final polymerization. The hyperbranched polymers were well characterized by ¹H NMR spectra and TD-SEC, and DBs of the polymers obtained are between 0.6 and 0.82, as well as the molar ratios of diacrylate/TMEA in the hyperbranched polymers are between 1.60 and 1.82. The fluorescence efficiency and quantum yields of HypET20, HypHT24 and HypDT24 has the following sequence: HypET20 > HypHT24 > HypDT24.     

Synthesis and properties of novel poly(coumarin‐amide)s

A novel monomer diacid, 6,6′‐methylenebis(2‐oxo‐2H‐chromene‐3‐carboxylic acid), was synthesized and used in a direct polycondensation reaction with various aromatic diamines in N‐methyl‐2‐pyrrolidone solution containing dissolved LiCl and CaCl₂, using triphenyl phosphite and pyridine as condensing agents to give a series of novel heteroaromatic polyamides containing photosensitive coumarin groups in the main chain. Polyamide properties were investigated by DSC, TGA, GPC, wide‐angle X‐ray scattering, viscosity, and solubility measurements. The copolymers were soluble in aprotic polar solvents, and their inherent viscosities varied between 0.49 and 0.78 dL g^?1. The weight‐average and number‐average molecular weights, measured by gel permeation chromatography, were 27,500–43,900 g mol^?1 and 46,500–66,300 g mol^?1, respectively, and polydispersities in the range of 1.48–1.69. The aromatic polyamides showed glass‐transition temperatures (T_g) ranging from 283 to 329°C and good thermal properties evidenced by no significant weight loss up to 380°C and 10% weight loss recorded above 425°C in air. All the polyamides exhibited an amorphous nature as evidenced by wide‐angle X‐ray diffraction and demonstrated a film forming capability. Water uptake values up to 3.35% were observed at 65% relative humidity. These polymers exhibited strong UV‐vis absorption maxima at 357–369 nm in DMSO solution, and no discernible photoluminescence maxima were detected by exciting with 365 nm. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Soluble semi-conductive chelate polymers containing Cr(III) in the backbone: Synthesis, characterization, optical, electrochemical, and electrical properties

Soluble kinds of coordination polymers containing Cr(III) ion in the backbone were synthesized. Structures of the polymers were characterized by FT-IR, UV-vis, ¹H and ¹³C NMR, and size exclusion chromatography (SEC). Thermal degradation data were obtained by TG-DTA and DSC techniques. Cyclic voltammetry (CV) measurements were carried out and the HOMO-LUMO energy levels and electrochemical band gaps were calculated. Additionally, the optical band gaps (E_g) were determined by using UV-vis spectra of the materials. Electrical conductivity measurements of doped (with iodine) and undoped polymers related to temperature were carried out by four-point probe technique using a Keithley 2400 electrometer. Measurements were made by using the polymeric films deposited on ITO glass plate by dip-coating method. Also, absorption spectra of doped polymeric films were recorded by a single beam spectrophotometer showing that doping procedure causes shifting in absorption spectra. Their abilities of processing in gas sensors were also discussed. According to obtained results the synthesized chelate polymers are semi-conductors having polyconjugated structures. Also, P-2 is the most electro-conductive polymer among the synthesized, while P-1 is the most thermally stable one.