Synthesis,characterization, thermal, and optical properties of conjugated copolymers derived from phenanthrene-9,10-dione- and dibenzo[f,h]quinoxaline

Donor–acceptor (D-A) conjugated polymers bearing phenanthrene-9,10-dione and dibenzo[f,h]quinoxaline as the acceptor units were synthesized via an optimized Suzuki cross-coupling reaction. Each of the aforementioned acceptors was reacted with three different donor comonomers, namely, fluorene, carbazole, and silafluorene derivatives, bearing long alkyl chains. The resulting copolymers display excellent solubility in common organic solvents with high chemical stability, allowing for the determination of their structural, thermal, and optical properties by various analytical techniques.     

An acceptor‐acceptor conjugated copolymer based on perylene diimide for high mobility n‐channel transistor in air

A new solution‐processable acceptor‐acceptor conjugated copolymer ( P1 ) based on perylene diimide (PDI) incorporating planar electron‐deficient fluorenone was synthesized by palladium(0)‐catalyzed Suzuki coupling reaction. Relative to the donor‐acceptor conjugated copolymer ( P2 ) of PDI and dithienothiophene, polymer P1 exhibits 0.1 eV down shift of lowest unoccupied molecular orbital (LUMO) level, 70 nm blue shift of low‐energy absorption band, and 0.36 eV increase of optical band gap. Polymer P1 in top‐contact bottom‐gate organic field‐effect transistors exhibits a saturation electron mobility of 0.01 cm²/(V s) in air, while P2 does not function in the same device in air. The better air stability of P1 is attributed to a more dense packing of the polymer chains excluding oxygen or water and lower LUMO level of P1 . © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis, Structure and Photophysical Properties of Silole-Oxadiazole Copolymers

A new conjugated copolymer (PTST‐DyOXD) derived from 1,1‐dimethyl‐3,4‐diphenyl‐2,5‐bis(5‐bromo‐2‐thienyl)‐silole (TST) and 2,5‐bis(4‐ethynylphenyl)‐1,3,4‐oxadiazole (DyOXD) was synthesized by Pd(0)‐catalyzed Sonogashira coupling reaction. For comparison, another copolymer without acetenyl group (PTST‐OXD) was also synthesized by Pd(0)‐catalyzed Suzuki coupling reaction. Chemical structures and optoelectronic properties of the copolymers were characterized by ¹H NMR, ¹³C NMR, IR, UV‐vis absorption, photoluminescence and cyclic voltammetry. The number‐average molecular weight (M_n) is 4010 Da for PTST‐DyOXD and 3890 Da for PTST‐OXD, respectively. The thermogravimetric analysis (TGA) measurements show that they have good thermal stability with decomposition temperature at 312 and 318°C, respectively. The optical band gap is 2.21 eV for PTST‐DyOXD and 2.10 eV for PTST‐OXD based on the absorption onset. CV analysis revealed the LUMO level of PTST‐DyOXD is ?3.04 eV, lower than that of PTST‐OXD (about ?2.89 eV), which is attributed to the introduction of acetylene group in PTST‐DyOXD, increasing the system of the conjugate chain length.     

Microwave-assisted Suzuki coupling on a KF-alumina surface: synthesis of polyaryls

A range of conjugated polyaryls has been synthesized through one-pot microwave assisted palladium-catalyzed consecutive Suzuki coupling reactions on a KF-alumina surface with notable features including rapid reaction times, solvent-free conditions, high yields, atom economic and air-insensitive reactions.     

Synthesis and characterization of soluble oligo (9,10-bisalkynylanthrylene)s

[structure: see text] Soluble oligo(9,10-bialkynylanthrylene)s up to pentamers were synthesized by means of the Suzuki coupling reaction. A solution processed thin film field-effect transistor from pentamer OA-5b shows a charge carrier mobility of 2.95 x 10(-)(3) cm(2)/V x s.     

Nanoporous phenanthroline polymer locked Pd as highly efficient catalyst for Suzuki-Miyaura Coupling reaction at room temperature

Because of the intrinsic advantages, Suzuki coupling reactions have been one of the most popular coupling reactions in organic synthesis, however developing a high-performance heterogeneous catalyst for Suzuki coupling reactions in aqueous media at low temperature (e.g. room temperature) is still a challenge. Herein, a heterogeneous catalyst with coordinated Pd as active site and a designed conjugated phenanthroline based porous polymer (CPP) as support was fabricated. Systematically investigation on CPP support by Fourier transform infrared spectroscopy (FT-IR), Thermogravimetric analysis (TGA), Transmission electron microscopy (TEM), N₂ adsorption–desorption isotherm and Scanning electron microscopy (SEM) show that the derived CPP catalyst support owns a porous structure, moderately good surface area (141 m²/g) and an excellent thermal stability. As a heterogeneous catalyst for the synthesis of biphenyl derivatives via Suzuki coupling, Pd/CPP achieves an excellent catalytic performance and recycling ability towards Suzuki reaction of various reactants at room temperature in ethanol-water medium.     

Preparation, photophysics, and electrochemistry of segmented comonomers consisting of thiophene and pyrimidine units: new monomers for hybrid copolymers

An efficient coupling route to novel pi-conjugated comonomers consisting of pyrimidine, thiophene, and bithiophene units was developed. The novel pi-donor-acceptor-donor and pi-donor-acceptor-acceptor-donor conjugated compounds were prepared by Suzuki heterocoupling and Ni(0)-mediated Ullman homocoupling reactions. Photophysical investigation of these alternating pi-donor and acceptor compounds indicated that the deactivation of their singlet excited state proceeds predominately by fluorescence and results in high fluorescence quantum yields. Intersystem crossing to the triplet state was also present in ca. 10%. Quantification of the triplet manifold by laser flash photolysis further revealed that bithiophene produced its triplet state in only 31%. Cyclic voltammetry studies showed that the comonomers undergo both oxidation and reduction leading to their radical cations and radical anions, respectively. The radical cations are highly reactive and undergo anodic polymerization resulting in mutual p- and n-type dopable polymers. The extended conjugation resulting from polymer formation was confirmed by both absorbance and fluorescence spectroscopy and by GPC. Ruthenium binding with the conjugated homocoupled ligand was also found resulting in a hybrid alternating copolymer with significantly different spectroscopic and electrochemical properties relative to its metal-free counterpart.     

新型以咔唑为主链的能量转移型发光聚合物

用Suzuki偶合反应合成了一系列以咔唑为主链，与不同的芳香环和杂环化合物 共聚的新型电致发光无规共聚物．这些共聚物溶于普通的有机溶剂，发较强的荧光 ．咔唑链段为共聚物提供了很好的空穴传输和空穴注入性能．与咔唑共聚的窄能隙 单体，如蒽(ANT)、噻吩(Th)、2，1，3-苯并噻二唑(BTDZ)、2，1，3—苯并硒二唑 (BseDZ)和4，7—二噻吩—2，1，3—苯并噻二唑(DBT)在聚合物中含量小于50％时 成为陷阱中心．还观察到极为有效的分子内能量转移．由于共聚单体的能隙不同， 这些电致发光共聚物的发光范围可覆盖整个可见光谱区．研究结果表明，用咔唑作 为宽带主体，与少量低带隙单体共聚，有可能成为一种合成同时兼有优异空穴注入 特性，又能广泛调节发光颜色的新的发光聚合物体系．     

Efficient and stable non-doped deep-blue organic light emitting diode based on an anthracene derivative

A new anthracene derivative 9,10-bis[3,5-di(4-tert-butylphenyl)phenyl]anthracene (BPPA) was synthesized via Suzuki coupling reaction and characterized by 1H NMR spectrum,mass spectrum,and elemental analysis.BPPA exhibits deep-blue emission both in solution and in solid thin film.This compound has a non-planar structure that results in high thermal stability and the phenomenon of polymorphism.The non-doped device based on this material shows stable deep-blue emission with the 1931 Commission international de...     

4-Carbomethoxybenzaldehyde as a highly sensitive pre-column fluorescence derivatization reagent for 9,10-phenanthrenequinone

9,10-Phenanthrenequinone (PQ) is harmful environmental pollutant that is detected in airborne particulates. The measurement of PQ in the air should be necessary to evaluate the potential adverse effects of PQ on human health. We have recently developed a determination method for PQ based on the fluorescence derivatization of PQ using benzaldehyde and ammonium acetate as a reagent. In this study, in order to obtain more sensitive and selective fluorescence derivatization reaction, we measured the fluorescence of the reaction mixture of PQ with 21 kinds of aromatic aldehydes in the presence of ammonium acetate. Among the tested aldehydes, 4-carbomethoxybenzaldehyde was found to be the best reagent in regard to fluorescence intensity and emission wavelength maximum. Based on the fluorescence derivatization with 4-carbomethoxybenzaldehyde, a highly sensitive chromatographic method was developed for the determination of PQ with the detection limit (S/N=3) of 1.2 fmol/injection.     

Preparation,morphology, and biolabeling of fluorescent nanoparticles based on conjugated polymers by emulsion polymerization

Novel nanoparticles based on conjugated polymer with good fluorescent properties were synthesized by Suzuki coupling reaction using certain surfactants as one kind of special emulsion polymerization. The luminescent properties of the prepared nanoparticles could be controlled by selecting different monomers. Without using substances comprising any heavy metal element, these fluorescent nanoparticles show very good biocompatibility with cells, thus showing potential applications in cell biolabeling, drug delivery tracing, organic light‐emitting diodes, flat displays, and other areas. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

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...     

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     

Room Temperature Anhydrous Suzuki–Miyaura Polymerization Enabled by C−S Bond Activation

The Suzuki–Miyaura cross-coupling is one of the most important and powerful methods for constructing C−C bonds. However, the protodeboronation of arylboronic acids hinder the development of Suzuki–Miyaura coupling in the precise synthesis of conjugated polymers (CPs). Here, an anhydrous room temperature Suzuki–Miyaura cross-coupling reaction between (hetero)aryl boronic esters and aryl sulfides was explored, of which universality was exemplified by thirty small molecules and twelve CPs. Meanwhile, the mechanistic studies involving with capturing four coordinated borate intermediate revealed the direct transmetalation of boronic esters in the absence of H₂O suppressing the protodeboronation. Additionally, the room temperature reaction significantly reduced the homocoupling defects and enhanced the optoelectronic properties of the CPs. In all, this work provides a green protocol to synthesize alternating CPs.     

Novel application of 1-/2-phenyl substituted 9,10-anthraquinones in solid electrochromic devices

1-/2-phenyl substituted 9,10-anthraquinones were synthesized via Suzuki coupling reactions of 1-/2-iodo-9,10-anthraquinones with benzeneboronic acid. They are efficient and reversible electrochromic materials and their solid electrochromic devices were prepared. When reduced, the device color of 1-phenyl-9,10-anthraquinone shifts from yellow to claret while that of 2-phenyl-9,10-anthraquinone switches from yellow-green to a dark blue-purple. Their different characteristics and behaviors in electrochromic devices are only determined by the different substituted positions of the phenyl group. They are potentially to be widely applied in commercial application for the excellent behaviors plus the inexpensive starting materials and short synthetic routes.     

Products of photoreduction of 9,10-phenanthrenequinone in the presence of N,N-dimethylanilines and polymethylbenzenes

Photoreduction of 9,10-phenanthrenequinone (PQ) in the presence of p-substituted N,N-dimethylanilines and polymethylbenzenes affords corresponding phenolethers as primary products. In the subsequent process shielded from light, phenolethers, which were formed by photoreaction of PQ with N,N-dimethylanilines, were quantitatively converted to give corresponding ketols. Phenolethers of 9,10-phenanthrenequinone and polymethylbenzenes are rearranged only under irradiation and in the presence of second molecule of PQ to form ketols. Stability of phenolethers is determined by redox properties and structure of hydrogen donors.     

Synthesis of n-type conjugated polymers for bulk heterojunction solar cells

A new conjugated alternating donor-acceptor copolymer is synthesized from perylene diimide and the benzodithiophene derivative via the Suzuki reaction. Temperatures corresponding to the 10% weight loss of the copolymer in air and argon are 336 and 362°C. The copolymer is soluble in common organic solvents. The maxima of absorption spectra of the copolymer in chloroform solution and thin films are at 456 and 567 and at 444 and 567 nm, respectively. The optical band gap, as calculated from the onset of the absorption spectrum, is 1.74 eV, and the electrochemical band gap is 1.89 eV. The energies of HOMO and LUMO derived from the onset of the first oxidation and reduction potential of the cyclic voltamperogram are ?5.97 and ?4.08 eV. It is found that the solar cell with copolymer-to-poly(3-hexylthiophene) = 1: 1 features the best characteristics: The open circuit voltage is 0.54 V, the short circuit current is 0.976 mA/cm², the fill factor is 0.397, and the efficiency is 0.14%. The conjugated polymer based on perylene diimide belongs to the class of n-type polymers and shows promise as an acceptor material for all-polymer bulk heterojunction solar cells.     

White light electroluminescence from graphene‐enhanced single polymer comprising two color emitters of equal molar ratios

White polymeric light‐emitting diode (WPLED) based on a single polymer, poly(3‐hexylthiophene‐alt‐9,9‐dioctylfluorene) (PTAF), has been successfully demonstrated. This conjugated alternating copolymer, PTAF, comprises 50 mol % of 3‐hexylthiophene which is an orange‐red color chromophore and 50 mol % 9,9‐dioctylfluorene which is a bluish‐green color chromophore. It was synthesized by Suzuki cross‐coupling reaction and has a molecular weight of 15,021 and polydispersity of 1.36. Nanocomposite consisting PTAF and graphene nanosheets enhances the optoelectronic properties and the device fabricated with a configuration of ITO/PEDOT:PSS/(PTAF + 1% graphene)/Ca/Al shows two‐color white electroluminescence with CIE 1931 coordinates of (0.28, 0.34). The white luminescence from a single polymer affords the WPLED device a simple structure and low fabrication cost. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

A general synthetic route to indenofluorene derivatives as new organic semiconductors

A series of 2,6-disubstituted indenofluorene derivatives were obtained in high purity via a general route involving the Suzuki coupling reaction. The potential of these conjugated indenofluorenes as new organic semiconductors was demonstrated by the light-emitting diode reaching a high luminance of 1400 Cd/m(2) below 10 V. [structure: see text]