基于氟代异靛蓝并[7,6-g]异靛蓝的共轭聚合物的合成及其半导体性质

采用Stille缩聚,合成了3个异靛蓝并[7,6-g]异靛蓝(DIID)和乙烯单元交替排列的共轭聚合物P0F、P2F和P4F,三者在DIID单元中分别含0、2和4个氟原子(F).3个聚合物均具有良好的平面性,前线分子轨道几乎在整个共轭骨架上离域.它们均具有宽的吸收光谱,吸收范围在400~1000 nm,光学带隙约为1.25 eV;随着氟原子数目的增加,聚合物的最高占有分子轨道(HOMO)和最低空分子轨道(LUMO)能级依次下降0.1~0.2 eV.以这3个聚合物作为活性层,制备了顶栅-底接触型有机场效应晶体管器件,随着氟原子数目的增加,聚合物的传输性质由双极传输变为n型传输.P0F和P2F是双极传输型聚合物,空穴迁移率(μ_h)分别达到0.11和0.30 cm~2 V~(-1) s~(-1),电子迁移率(me)分别达到0.22和1.19 cm~2 V~(-1) s~(-1).P4F是n型聚合物,me达到0.18 cm~2 V~(-1) s~(-1).     

Extended triphenylamine conjugated systems derivatized by perfluorophenyl groups

Two triphenylamine derivatives bearing terminal perfluorophenyl groups have been synthesized. Their HOMO, LUMO levels and electronic band gap have been evaluated by spectroscopic and electrochemical measurements and rationalized with theoretical calculations. X-ray structure analysis of crystals allowed the observation of multiple intermolecular interactions due to the presence of the perfluorophenyl pendant groups. The multiplication of these interactions explains the differences between calculated (in gas phase) and observed (in solid states) structures.     

Stacked 1,3,5-tris[(2,5-dimethylphenyl)ethynyl]benzenes: dimer and conjugated microporous polymer

A new [2.2]paracyclophane compound consisting of two 1,3,5-tris[(2,5-dimethylphenyl)ethynyl]benzenes stacked in proximity to each other. The compound exhibited a unique absorption band (cyclophane band) and an emission from the phane state, both of which were derived from the π-π stacking of the poorly extended conjugation systems of 1,3,5-tris[(2,5-dimethylphenyl)ethynyl]benzene. In addition, a conjugated microporous polymer (CMP) that comprises pseudo-para-substituted [2.2]paracyclophane was prepared. The obtained CMP is regarded as a polymer, in which 1,3,5-tris[(2,5-dimethylphenyl)ethynyl]benzenes are infinitely stacked to form a network structure. The CMP exhibited a type I nitrogen gas sorption profile and an H4-like hysteresis loop, and possessed the slit-like mesopores with a BET surface area of 501 m² g⁻¹.     

Synthesis and characterization of novel conjugated polymers based on 3-cyclobutene-1,2-dione moiety

Three novel conjugated polymers bearing 3,4-bis（4-hexylthiophen-2-yl）-3-cyclobutene-1,2-dione unit in their main chain have been synthesized successfully in good yields through Suzuki or Stille coupling reaction.Their molecular structures have been confirmed by FT-IR,¹H NMR and ¹³C NMR.All these copolymers exhibit broad and strong absorption bands in UV-vis region,and their optical band gaps are calculated to be 1.6-2.0 eV.suggesting that they have good coverage with the solar spectrum.These polymers have good thermostability and solubility in common organic solvents.Moreover,all these objective macromolecules possess high electron affinity of～3.8 eV determined from cyclic voltammetry measurement,implying that they are potential n-type polymeric photovoltaic materials.     

Synthesis and characterization of novel conjugated polymers based on 3-cyclobutene-l,2-dione moiety

Three novel conjugated polymers bearing 3,4-bis(4-hexylthiophen-2-yl)-3-cyclobutene-1,2-dione unit in their main chain have been synthesized successfully in good yields through Suzuki or Stille coupling reaction.Their molecular structures have been confirmed by FT-IR,~1H NMR and ~(13)C NMR.All these copolymers exhibit broad and strong absorption bands in UV-vis region,and their optical band gaps are calculated to be 1.6-2.0 eV.suggesting that they have good coverage with the solar spectrum.These polymers...     

Synthesis and investigation of photovoltaic properties for polymer semiconductors based on porphyrin compounds as light-harvesting units

We reported on two polymer semiconducting copolymers based on porphyrin compounds, poly[9,9-dioctylfluorene-co-5,15-bis(hexoxybenzyl)-10,20-bis(benzo-4-yl)porphyrin] (PFPor) and poly[9-(heptadecan-9-yl)carbazole-co-5,15-bis(hexoxybenzyl)-10,20-bis(benzo-4-yl)porphyrin] (PCPor), for use as organic photovoltaic materials. The thermal, optical, electrochemical, and photovoltaic properties of the two polymers were investigated. In addition, PC₆₁BM and PC₇₁BM were introduced as acceptor materials to confirm the acceptor effect in bulk heterojunction photovoltaic devices. Moreover, in order to establish acceptor effects, morphologies of polymer/PCBM blend films were analyzed through atomic force microscopy (AFM). PFPor and PCPor exhibited the best device performance with power conversion efficiencies (PCE) of 0.62% and 0.76%, respectively, upon the introduction of PC₇₁BM as the acceptor in the device where 86 wt.% of the PC₇₁BM was contained in the active layer (pol:PC₇₁BM = 1:6, w/w).     

An IR study of poly-1,4-phenylenevinylene (PPV), the 2,5-dimethoxy derivative [(MeO)2-PPV], and their corresponding xanthate precursor polymers and monomers

A detailed comparison of the infrared (IR) spectra of poly-1,4-phenylenevinylene (PPV), its xanthate precursor polymer, and its bis-xanthate precursor monomer along with the corresponding 2,5-dimethoxy derivatives has provided a clearer basis for characterizing these species with regard to both structure and purity. All the xanthate precursor monomers and polymers exhibit characteristic intense absorptions typical of the xanthate group near 1220, 1110, and 1050 cm(-1). Upon complete conversion of the precursor polymer to the vinylene linked final product, the intense IR peaks of the xanthate group have disappeared and new bands resulting from the vinylene linkages are found. The latter include a moderately strong band near 965 cm(-1) due to the out-of-plane -CHCH- deformation of the trans-vinylene conjugated with and linking the phenyl rings into an optoelectronic polymer. Unfortunately, the corresponding C-H stretching vibration of this same group of atoms expected to appear near 3020 cm(-1) falls in the same region of the spectrum as the aromatic C-H stretches of the phenyl rings. Similarly, for the 2,5-dimethoxy polymer derivative, [(MeO)(2)-PPV], the C-H stretching vibration near 3055 cm(-1) contains contributions from both aromatic and vinylene C-H. Density functional theory (DFT) calculations on the monomers were instrumental in assigning the infrared spectra of these materials. This study provides a systemic means for verifying that the precursor monomer has been polymerized into the precursor polymer and that thermal conversion to the conjugated polymer is complete.     

Copolymerization of benzoquinone with norbornene

For the first time, the conjugated dicarbonyl compound benzoquinone has been copolymerized with the strained cyclo-olefin norbornene using catalytic amounts of the Friedel-Crafts metathesis catalytic system WOCl₄+AlCl₃. All analyses reveal that the products consist of conjugated blocks originating from benzoquinone connected with spacers originating from norbornene. The products are soluble in benzene, toluene, chlorobenzene, etc. but possess properties of the conjugated polymers. They have been synthesized via a very simple one-pot procedure.     

Third-order nonlinear optical studies of newly synthesized polyoxadiazoles containing 3,4-dialkoxythiophenes

The third-order nonlinear optical properties of newly synthesized soluble polyoxadiazoles containing 3,4-dialkoxythiophenes were investigated by using Z-scan and degenerate four-wave mixing (DFWM) techniques. The measurements were performed at 532 nm with 7 ns pulses from a Nd:YAG laser. We found a good agreement between the values of χ⁽³⁾ determined from both the experiments. Z-scan results indicate a negative nonlinear refractive index, n₂, whose magnitude is of the order of 10⁻¹⁰ esu for all the copolymers. The variation of nonlinear response among the copolymers clearly indicates the dependence of χ⁽³⁾ on donor and acceptor type of units present in these copolymers. The copolymers exhibit strong reverse saturable absorption and good optical limiting properties at 532 nm.     

Correlation between spectroscopic and morphological properties of composite P3HT/PCBM nanoparticles studied by single particle spectroscopy

We report the fabrication and characterization of composite nanoparticles consisting of a conducting polymer, poly-3-hexylthiophene (P3HT), doped with varying amounts of [6,6]-phenyl C61-butyric acid methyl ester (PCBM), a material blend that is commonly applied in bulk heterojunction organic photovoltaic devices (OPVs). Single particle spectroscopy (SPS) studies, where nanoparticles are studied one particle at a time, reveal that these nanoparticles have spectroscopic characteristics consistent with the existence of two types of crystalline nanodomains, one with a higher energy emission at 660 nm and one with a lower energy emission at 720 nm. In addition, the occurrence of emission at lower peak energy increases with increasing PCBM doping levels, and the intensity of the lower energy peak emission increases with respect to the higher energy peak emission as well. These data reveal a PCBM concentration dependent formation of two types of P3HT crystalline nanodomains in P3HT/PCBM composite nanoparticles, where the lower energy crystal structure becomes more favored with higher PCBM concentration. This work provides a molecular scale insight in the correlation between changes in morphology of conjugated polymer materials with different weight percentages of fullerene dopants.