Synthesis and characterization of dithienylbenzobis(thiadiazole)-based low band-gap polymers for organic electronics

New donor-acceptor alternating conjugated polymers were synthesized and characterized. Among them, PCPBBT exhibited a band-gap of 1.01 eV and ambipolar characteristics with μ(h) = 7.1 × 10(-4) cm(2) V(-1) s(-1) and μ(e) = 3.3 × 10(-3) cm(2) V(-1) s(-1).     

SYNTHESIS AND CHARACTEAIZATION OF POLY(PYRROLY METHINE)

A novel small band-gap conjugated polymer - poly [(3-acetylpyrrole-2, 5-diyl)(4-dimethylaminobenzyliene)(3 -acetylpyrrolequinodimethane-2, 5-diyl)] (PAPDMABE) - and its precursor were synthesized by a simple method andcharacterized by ~1H-NMR, FT-IR, TGA and UV-VIS. The polymer can be dissolved in strong polar solvents such as DMSO,DMF or NMP. The band-gap energy of PAPDMABE was found to be 0.95 eV. The conductivity of doped products withiodine falls in the range of a semiconductor.     

Incorporation of furan into low band-gap polymers for efficient solar cells

The design, synthesis, and characterization of the first examples of furan-containing low band-gap polymers, PDPP2FT and PDPP3F, with substantial power conversion efficiencies in organic solar cells are reported. Inserting furan moieties in the backbone of the conjugated polymers enables the use of relatively small solubilizing side chains because of the significant contribution of the furan rings to overall polymer solubility in common organic solvents. Bulk heterojunction solar cells fabricated from furan-containing polymers and PC(71)BM as the acceptor showed power conversion efficiencies reaching 5.0%.     

Increased open circuit voltage in fluorinated benzothiadiazole-based alternating conjugated polymers

Small band-gap conjugated polymers based on monofluoro- and difluoro-substituted benzothiadiazole were developed. Highly efficient polymer solar cells (PCE as high as 5.40%) could be achieved for devices made from these polymers.     

含联芴烯单元共轭聚合物的合成及表征

以六羰基钨[W(CO)₆]为催化剂, 合成了聚吲哚芴(P1)、 聚梯型四苯(P2)、 聚梯型五苯(P3)和小分子9-联吲哚芴烯(S1).该类聚合物的重复单元含有联芴烯结构, 通过芴9位的双键连接. 光学和电化学等实验结果表明, 聚合物无荧光发射, 是一类窄带隙的共轭聚合物, 其中聚合物P1薄膜的紫外吸收值最大波长为710 nm.     

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).     

含二呋喃基苯并噻二唑的聚芳炔类衍生物的合成与性能

以四(三苯基磷)钯(Pd(PPh3)4)和CuI为催化剂,在二异丙胺和四氢呋喃溶液中,采用宽能带的1,4-二乙炔基-2,5-二(十二烷氧基)苯(PE)和窄能带的4,7-双(5′-溴-2′-呋喃)-2,1,3-苯并噻二唑(FBT)合成了一系列新型聚芳炔。长链烷氧基的存在使得此类聚合物在常用的有机溶剂中具有较好的溶解性和成膜性。通过对上述聚合物的紫外-可见吸收、荧光发射及循环伏安等基本性能进行探讨可知,随着共聚物中FBT含量的增加,共聚物薄膜的吸收起始波长及荧光发射波长均有明显的红移。聚合物薄膜的最大发射峰位于600～650 nm,聚合物中的能量能有效地由PE单元转移到FBT单元上。     

Effect of Side Chain Substituent Volume on Thermoelectric Properties of IDT-Based Conjugated Polymers

A p-type thermoelectric conjugated polymer based on indacenodithiophene and benzothiadiazole is designed and synthesized by replacing normal aliphatic side chains (P1) with conjugated aromatic benzene substituents (P2). The introduced bulky substituent on P2 is detrimental to form the intensified packing of polymers, therefore, it hinders the efficient transporting of the charge carriers, eventually resulting in a lower conductivity compared to that of the polymers bearing aliphatic side chains (P1). These results reveal that the modification of side chains on conjugated polymers is crucial to rationally designed thermoelectric polymers with high performance.     

Efficient Pictet–Spengler Bioconjugation with N‐Substituted Pyrrolyl Alanine Derivatives

We discovered N‐pyrrolyl alanine derivatives as efficient reagents for the fast and selective Pictet–Spengler reaction with aldehyde‐containing biomolecules. Other aldehyde‐labeling methods described so far have several drawbacks, like hydrolytic instability, slow reaction kinetics or not readily available labeling reagents. Pictet–Spengler cyclizations of pyrrolyl 2‐ethylamine substituted at the pyrrole nitrogen are significantly faster than with analogues substituted at the α‐ and β‐ position. Functionalized N‐pyrrolyl alanine derivatives can be synthesized in only 2–3 steps from commercially available materials. The small size of the reagent, the high reaction rate, and the easy synthesis make pyrrolyl alanine Pictet–Spengler (PAPS) an attractive choice for bioconjugation reactions. PAPS was shown as an efficient strategy for the site‐selective biotinylation of an antibody as well as for the condensation of nucleic‐acid derivatives, demonstrating the versatility of this reagent.     

A low band-gap polymer based on unsubstituted benzo[1,2-b:4,5-b']dithiophene for high performance organic photovoltaics

A low band-gap conjugated polymer, PBDTDPP, composed of unsubstituted benzo[1,2-b:4,5-b']dithiophene and diketopyrrolo[3,4-c]pyrrole was synthesized. The deep HOMO level of PBDTDPP enhances the V(OC) of a PSC up to 0.82 V and exhibits a PCE of 5.16%, while alkoxy substituted PBDTDPP-OR yields a PCE of 2.24% with a V(OC) of 0.61 V.     

Polymerization of 1,4-bis[2-(N-vinyl)pyrrolyl]benzene

Polymers of 1,4-bis[2-(N-vinyl)pyrrolyl]benzene with free N-vinyl groups in side chains are synthesized in the presence of AIBN (2–5 wt %, 70°C) with a yield of up to 34% and a molecular mass of up to 11.5 × 10³. In the presence of cationic catalysts (Me₃SiCl, the LiBF₄-dimethoxyethane system, and BF₃ · OEt₂), 1,4-bis[2-(N-vinyl)pyrrolyl]benzene gives macromolecules with alternating 1,2-pyrrolene and ethylidene units in the backbone with yields of 80, 44, and 33%, respectively. The polymers demonstrate paramagnetic and luminescent properties.     

Halogenated benzothiadiazole-based conjugated polymers as efficient photocatalysts for dye degradation and oxidative coupling of benzylamines

Donor-acceptor(D-A) conjugated polymers are widely used in photovoltaic applications and heterogeneous catalysis due to their tunable building block and pre-designable structures. Here, a series of adjustable Donor-acceptor(D-A) benzothiodiazole-based conjugated polymers were designed and synthesized. The photocatalytic performance could be improved by fine-tuning the chemical structure by halogen substitution(F or Cl). The polymers exhibited excellent optoelectronic properties and were effectiv...     

Synthesis of Layered Carbonitrides from Biotic Molecules for Photoredox Transformations

The construction of layered covalent carbon nitride polymers based on tri-s-triazine units has been achieved by using nucleobases (adenine, guanine, cytosine, thymine and uracil) and urea to establish a two-dimensional semiconducting structure that allows band-gap engineering applications. This biomolecule-derived binary carbon nitride polymer enables the generation of energized charge carrier with light-irradiation to induce photoredox reactions for stable hydrogen production and heterogeneous organosynthesis of C−O, C−C, C−N and N−N bonds, which may enrich discussion on chemical reactions in prebiotic conditions by taking account of the photoredox function of conjugated carbonitride semiconductors that have long been considered to be stable HCN-derived organic macromolecules in space.     

One‐step synthesis of a thienylenepyridazinylenethienylene‐based coil‐rod‐coil copolymer with enhanced emission and improved fluorescence stability

A new coil‐rod‐coil copolymer is synthesized via Sonogashira coupling using one‐step methodology. The copolymer PEG‐OEPETPT‐PEG constitutes of poly(ethylene glycol) (PEG) as the coil block, and oligo[p‐(ethynylenephenyleneethynylene)‐alt‐(thienylenepyridazinylenethienylene)] (OEPETPT) as the rod segment. The conjugated polymer PEPETPT with the same conjugated building blocks is also synthesized for comparison. The structures of both polymers are confirmed by NMR, combined with other characterizations. PEG‐OEPETPT‐PEG has a 12 nm blue‐shift in the emission maximum compared with that of PEPETPT, and a higher quantum yield of fluorescence in THF. PEG‐OEPETPTE‐PEG tolerates up to 20% water content in H₂O/THF mixed solvent without significantly changing the emission wavelength and intensity, while the fluorescence of PEPETPT is dramatically quenched by a very small quantity of water. Further photophysical studies about these two polymers indicate that the introduction of PEG coils onto the conjugated block retards the water‐induced‐aggregation and therefore improves the fluorescence stability of PEG‐OEPETPT‐PEG. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

共轭刚性苯并二噁唑类聚合物的合成及其光物理性能研究

设计并合成了一系列共轭高分子———聚亚苯基苯并二唑 (PBO) ,聚亚乙烯基苯并二唑 (PBOV)和聚亚丁二唑 (PBODV) ,并对它们进行了表征 .用紫外吸收光谱和荧光光谱对聚合物的溶液和薄膜进行了详细的研究 ,研究结果表明分子结构中双键的引入可以降低聚合物的光带能隙 ,λmax从PBO溶液的 4 2 8 5nm (Eg=2 76eV) ,到PBOV溶液的 4 80 5nm (Eg=2 4 6eV) ,再到PBODV溶液的 4 96 0nm (Eg=2 38eV) .共轭程度的增加使得聚合物溶液更容易发生集聚从而导致荧光自熄灭 .     

High charge carrier mobility in conjugated organometallic polymer networks

The improvement of charge transport in conjugated polymers is a focal point of current research. It is shown here that the carrier mobility can be substantially increased through the introduction of conjugated cross-links between the conjugated chains. Novel organometallic polymer networks based on a poly(p-phenylene ethynylene) (PPE) derivative and Pt0 were synthesized by ligand-exchange reactions between the linear PPE and a low-molecular Pt complex. Time-of-flight measurements revealed ambipolar charge carrier mobilities of up to 1.6 x 10-2 cm2 V-1 s-1 for these materials, which are an order of magnitude higher than those of the neat polymer and represent the highest mobilities yet observed in disordered conjugated polymers.     

规整链球型含C_(60)聚苯乙烯的亲水化修饰及其在水中的自组装

C60作为碳的第三种同素异型体,一经发现就为当今科学研究所关注.其独特的光学,电学性能吸引了许多化学工作者的不懈努力,以探索其在化学、材料科学等领域的应用.精确的化学修饰不仅是改善其较差的溶解和加工性能的主要途径之一,而且更能提供规整的结构,以利于对其性能的深入研究.     

新型共轭高分子聚[吡咯2,5-二(3-甲氧基-4-羟基苯甲烯)]的合成与表征

本文采用两步法合成了一种新型共轭高分子聚 [吡咯 2 ,5 二 (3 甲氧基 4 羟基苯甲烯 ) ],其前聚物聚 [吡咯 2 ,5 二 (3 甲氧基 4 羟基苯甲烷 ) ]可溶于一般的极性有机溶剂 .通过红外、核磁、紫外光谱分析鉴定了产物及其前聚物的结构 .利用DSC与TGA测试分析了所合成聚合物的热学性质 .紫外光谱表明在聚合物链中引入醌式吡咯环结构有利于降低产物的能隙 ,其能隙为 1 14eV ,属窄能隙类共轭聚合物 .经碘掺杂后产物的电导率在半导体的范围内     

荧光共轭聚合物在生物大分子检测中的应用*

共轭聚合物因其具有π-电子体系及共轭离域结构,一般都具有优异的发光性能,其发光强度和发射波长会随被检测化合物结构的不同而发生特异性响应,特别是在与被检测物相互作用过程中所产生电荷和能量能够沿共轭分子链进行有效传递,成倍放大这种作用,从而有效提高了检测灵敏度,这比相应的小分子化合物更具有优越性。目前共轭聚合物已被用于开发新型化学、生物传感器,尤其是在生物分子检测方面的应用得到迅速的发展。本文总结了近年来荧光共轭聚合物在生物传感方面的研究进展,主要讨论共轭聚合物在蛋白质、核酸及毒素检测中的应用。     

Synthesis and characterization of 5-octylthieno[3,4-c]pyrrole-4,6-dione derivatives as new monomers for conjugated copolymers

An efficient route for the synthesis of 1-iodo-5-octyl-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione as a key intermediate to build new electron-deficient monomers and related conjugated polymers is reported. Along these lines, two new low bandgap copolymers were synthesized from Stille or Suzuki coupling. These polymers were characterized and their properties compared to those of analogous conjugated polymers.