硒吩聚合物/寡聚物有机光电材料研究进展

主要从光电性能角度总结了近几年硒吩聚合物/寡聚物在有机太阳能电池(OSCs)、场效应晶体管(FETs)、发光二级管(LED)等方面的研究进展。目前,基于聚硒吩并[3,4-b]硒吩-苯并二硒吩(PSeB2)(polyselenopheno[3,4-b]selenophene-co-benzodiselenophene)本体异质结太阳能电池器件的能量转化效率最高,达6.87%;场效应晶体管方面,基于PSeDPP(P28)器件的空穴迁移率最高达1.62cm2.V-1.s-1。基于PFO-DDSTQ(一种硒吩芴基聚合物)的发光二级管,表现出目前基于硒吩化合物的最长波长发光器件,EL光谱峰值约860nm。通过对研究者的研究成果的总结发现,在有机光电器件的应用领域中硒吩聚合物/寡聚物是一种极具应用前景的材料。     

全共轭聚噻吩类和聚硒吩类嵌段共聚物的凝聚态结构调控

嵌段共聚物可发生微相分离形成丰富的介观尺度上的相结构,而共轭聚合物是一类具有特殊的力学、导电性能或光电功能的半刚性链高分子.全共轭嵌段共聚物因其兼具两者的特性而备受瞩目.本文着重介绍了近年来课题组在基于全共轭聚(3-烷基噻吩)和聚(3-烷基硒吩)嵌段共聚物体系的研究进展,通过改变体系的分子结构包括主侧链结构、侧链的烷基长度及取代基团等以及对体系在溶液状态及薄膜状态进行后处理包括改变溶剂、热处理、溶剂蒸气处理等来调控体系的微相分离行为和结晶行为,实现对材料凝聚态结构的调控.在此基础上,以有机场效应晶体管和聚合物太阳能电池器件作为最终体现聚噻吩或聚硒吩类体系凝聚态结构与性能关系的平台,将获得的调控体系凝聚态结构的有效策略用于实现其半导体材料物理性能的提升.     

聚并硒吩导电高聚物的电子结构及其掺杂导电机制的探究

聚并硒吩导电高聚物的电子结构及其掺杂导电机制的探究徐龙君，林宪杰（重庆大学化学系，重庆６３００４４）（菏泽师专化学系，菏泽２７４０１５）王荣顺（东北师大化学系，长春１３００２４）关键词：硒吩，导电高聚物，ＥＨＭＯ。聚并硒吩包括聚吡咯并［３．２－ｂ］硒...     

含苯并硒二唑聚咔唑/芴类共轭聚电解质及其前驱体的合成与性能研究

采用Suzuki偶合反应合成了一系列新型的咔唑、芴和2,1,3-苯并硒二唑的共聚物——聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并硒二唑-9,9-双(N,N-二甲基胺丙基)芴](PCzN-BSeD)及其相应的聚电解质衍生物——聚[3,6-(N-(2-乙基己基))咔唑-2,1,3-苯并硒二唑-9,9-(双(3′-(N,N-二甲基)-N-乙基铵)丙基)芴]二溴(PCzNBr-BSeD).在聚咔唑和芴中引入不同比例的2,1,3-苯并硒二唑(BSeD)单元,引起了由咔唑和芴链段向窄带隙苯并硒二唑(BSeD)单元有效的能量转移.通过对聚合物电致发光性能的研究,发现用聚(3,4-亚乙基二氧基噻吩)(PEDOT)或聚(3,4-亚乙基二氧基噻吩)/聚乙烯咔唑(PEDOT/PVK)作为空穴传输层时,器件的性能相差不大,表明咔唑的引入较明显的改善了聚合物的空穴注入性能.而且几乎所有的聚合物用高功函数铝作阴极的器件和用钡/铝作阴极的器件具有相近的发光性能,表明这类聚合物具有良好的电子注入性能.     

基于侧链为烷基硫苯的萘二酰亚胺单元的新型聚合物受体的合成及其光电性能

以N-（4-巯基苯基）乙酰胺、7-（溴甲基）十五烷和二溴萘二羧酸酐为原料合成了侧链为烷基硫苯的萘二酰亚胺（NDI）衍生物,将其作为受体单元,硒吩衍生物为给体单元,合成了基于NDI的新型聚合物受体(PNDI PSHD),同时合成了基于苯并二噻吩的D-A型共聚物PBDT(T) TPD作为给体材料,将聚合物给体、受体混合制备聚合物太阳能器件。聚合物的结构和光电性能经¹H NMR、 GPC、 UV、 CV和荧光发射光谱表征,并测试了器件的光伏性能。结果表明：给受体聚合物均具有较高的相对分子量,在太阳光范围具有强而宽的吸收,同时具有相对较低的最高电子占用轨道（HOMO）和最低电子未占用轨道（LUMO）能级,给受体聚合物混合后引起荧光猝灭,器件的能量转换效率（PCE）达到0.72%。     

综合研究DPE添加剂对含5,6-二氟-苯并[1,2,5]噻二唑给-受体共聚物的光伏性能影响（英文）

合成了三个以5,6-二氟-苯并[1,2,5]噻二唑为受体,2,5-双-(2-辛基-十二烷氧基)-1,4-双(噻吩并[3,2-b]噻吩基)苯和2,5-双-(2-辛基-十二烷氧基)-1,4-双(硒吩基)苯为给体的给-受体型共聚物(PBT2F-TT-a,PBT2F-TT和PBT2F-Se).这三个聚合物与PC71BM共混制备成了本体异质结聚合物太阳能电池.通过原子力显微镜(AFM)、透射电子显微镜(TEM)、交流阻抗谱(ACIS)、空间电荷限制电流(SCLC)和短路电流密度-入射光光强(JSC-Plight)测试方法系统研究了二苯醚(DPE)对活性层的形貌、载流子迁移率以及光伏性能的影响.实验结果表明DPE有助于提高共混膜载流子的迁移率,同时器件的光伏性能也得到改善.此外,PBT2F-Se器件的SCLC实验数据揭示了平衡的空穴和电子迁移率有利于提高器件的短路电流密度.     

综合研究DPE添加剂对含5,6-二氟-苯并[1,2,5]噻二唑给-受体共聚物的光伏性能影响

合成了三个以5,6-二氟-苯并[1,2,5]噻二唑为受体,2,5-双-（2-辛基-十二烷氧基）-1,4-双（噻吩并[3,2-b]噻吩基）苯和2,5-双-（2-辛基-十二烷氧基）-1,4-双（硒吩基）苯为给体的给-受体型共聚物（PBT2F-TT-a,PBT2F-TT和PBT2F-Se）.这三个聚合物与PC₇₁BM共混制备成了本体异质结聚合物太阳能电池.通过原子力显微镜（AFM）、透射电子显微镜（TEM）、交流阻抗谱（ACIS）、空间电荷限制电流（SCLC）和短路电流密度-入射光光强（J_SC-P_light）测试方法系统研究了二苯醚（DPE）对活性层的形貌、载流子迁移率以及光伏性能的影响.实验结果表明DPE有助于提高共混膜载流子的迁移率,同时器件的光伏性能也得到改善.此外,PBT2F-Se器件的SCLC实验数据揭示了平衡的空穴和电子迁移率有利于提高器件的短路电流密度.     

丙烯腈类共聚物膜用于醇,水分离的研究：Ⅱ.丙烯腈与马来酸酐…

本文采用氧化还原引发体系合成了丙烯腈与马来酸酐共聚物，各首次将此共聚物制成了醇，水分离用的渗透蒸发膜，研究了不同马来酸酐含量的共聚物膜碱中的水解规律，考察了共聚物，料液温度，料液浓度等条件对膜的醇，水分离性能的影响关系以及水解前，后膜性能的变化结果表明，当共聚物中马来酸酐含量大于０．０６９（摩尔分数）时，水解前，后膜性能有很大的变化，分离因子，渗透通量和膜强度都普遍提高。另外，还发现该共聚物膜与其     

一种基于聚噻吩-聚硒吩全共轭嵌段共聚物的合成及性质研究

全共轭刚性-刚性嵌段共聚物兼具嵌段共聚物的微相分离特性和共轭聚合物的光电性能，引起了人们越来越多的关注.基于此，我们利用格氏置换（GRIM）方法合成了全共轭刚性-刚性嵌段共聚物聚（3-己基硒吩）-b-聚（3-（6-羟基）-己基噻吩）（P3HS-b-P3HHT）.通过在噻吩段的烷基侧链末端引入羟基基团来丰富全共轭体系的溶液结构，并利用羟基的热交联特性提高聚噻吩均聚物的薄膜场效应晶体管的热稳定性.一方面，通过溶剂共混（氯仿/吡啶和甲醇/吡啶混合溶剂），调控P3HS-b-P3HHT分子在混合溶剂中的刚性-刚性相互作用，使P3HS-b-P3HHT在混合溶剂中自组装形成不同的纳米结构，如纳米带、纳米纤维和纳米微球等.另一方面，将P3HS-b-P3HHT和聚（3-己基噻吩）（P3HT）共混，利用羟基之间的热交联，使P3HS-b-P3HHT/P3HT共混薄膜在薄膜场效应晶体管中表现出较好的热稳定性.     

2,1,3-苯并硒二唑与联苯二胺类共轭共聚物的金属催化法合成与表征

利用金属催化法分别合成出了2,1,3-苯并硒二唑与N,N′-二氯联苯醌二亚胺、3,3′-二甲基-N,N′-二氯联苯醌二亚胺,3,3′-二甲氧基-N,N′-二氯联苯醌二亚胺的共轭交替共聚物:聚(N,N′-联苯醌二亚胺-2,1,3-苯并硒二唑),聚(3,3′-二甲基-N,N′-联苯醌二亚胺-2,1,3-苯并硒二唑),聚(3,3′-二甲氧基-N,N′-联苯醌二亚胺-2,1,3-苯并硒二唑)。利用凝胶色谱(GPC)、红外光谱、紫外可见光谱以及循环伏安(CV)等对这三种共聚物进行了表征和性能研究。紫外可见光谱分析结果表明,这三种共聚物分别在305nm、421nm,325nm、438nm和330nm、558nm处出现吸收峰,但由于受侧基的影响,聚(3,3′-二甲氧基-N,N′-联苯醌二亚胺-2,1,3-苯并硒二唑)相对于聚(N,N′-联苯醌二亚胺-2,1,3-苯并硒二唑)和聚(3,3′-二甲基-N,N′-联苯醌二亚胺-2,1,3-苯并硒二唑)的共轭程度要高,而且共聚物链上的侧基对其电化学性能也有一定的影响。     

Synthesis of benzo[b]selenophene and its methyl homologs

A method for the synthesis of benzo[b]selenophenes was perfected. 3-Oxo-2,3-dihydrobenzo[b]selenophene and 2-methyl-3-oxo-2,3-dihydrobenzo[b]selenophene exist only in the keto form. 3-Methylbenzo[b]selenophene was obtained by the reaction of 3-oxo-2,3-dihydrobenzo[b]selenophene with methylmagnesium iodide. Metallation of benzo[b]selenophene with butyllithium proceeds at the 2 position of the selenophene ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1475–1480, November, 1970.     

A theoretical study of nuclear spin coupling constants and hyperfine coupling constants of se-heterocyclics

MO calculations based on the finite perturbation theory in the INDO approximation have been carried out on selenophene, eighteen of its monosubstituted derivatives and benzo (b)selenophene. The calculated nuclear spin coupling constants satisfactorily reproduce signs, magnitudes, internal orders and some trends of the experimental values. Comparison of different ZDO calculations provides information on the relative importance of σ and π pathways for the various coupling constants in selenophene and benzo(b)selenophene. Unrestricted Hartree-Fock calculations at the INDO level have been performed on the radical anions of dibenzoselenophene and 2,1,3-benzoselenadiazole, the phenoselenazine radical cation, the phenoselenazine neutral radical and the phenoselenazine nitroxide. The isotropic hyperfine coupling constants have been found to be generally in satisfactory agreement with experiment.     

Light‐emitting copolymers based on fluorene and selenophene—Comparative studies with its sulfur analogue: Poly(fluorene‐co‐thiophene)

A series of soluble conjugated copolymers derived from 9,9‐dioctylfluorene (FO) and selenophene (SeH) was synthesized by a palladium‐catalyzed Suzuki coupling reaction with various feed ratios of SeH to FO less than or equal to 50%. The efficient energy transfer from fluorene segments to narrow band‐gap selenophene sites was observed. In comparison with the very well studied copolymer poly(fluorene‐co‐thiophene), poly(9,9‐dioctylfluorene‐co‐selenophene) (PFO‐SeH) shows redshifted photoluminescence (PL) and electroluminescence (EL) emission. PL spectra of the PFO‐SeH copolymers show a significant redshift along with increasing selenophene content in the copolymers and also with increasing polymer concentration in solution. PL quantum efficiency of the selenophene‐containing PFO copolymer is much lower than that of corresponding PFO‐thiophene (Th) copolymers. All these features of PFO‐SeH copolymers can be explained by the difference in aromaticity of selenophene and thiophene heterocycles and the heavy atom effect of Se in comparison with S‐atoms. The device fabricated with PFO‐SeH15 as the emissive layer exhibited high external quantum efficiency (0.51%) at a luminance of 1570 cd/m². Device performance is limited by electron injection and the strong quenching effect of Se atoms. Devices with PFO‐SeH copolymers blended into PFO homopolymers show significant improvement in device performance. External quantum efficiency as high as 1.7% can be obtained for PFO‐SeH30/PFO blend devices. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 823–836, 2005     

Infrared spectra of chalcone analogs containing the selenophene nucleus

The IR spectra of 30 chalcone analogs containing a selenophene nucleus have been measured in the 1800-500 cm^–1 region and an assignment of frequencies has been carried out. It has been confirmed that the selenophene radical in the static state has a greater electrondonating influence than the furyl and thienyl radicals. A linear relationship has been found between the shift of the frequency of the stretching vibrations of the carbonyl (v _C=O) under the influence of substituents in the 1-(selenien-2-yl)-3-arylpropenones and the parameters of Hammett's equation. The absorption curve of analogous compounds of the selenophene and thiophene series have been compared. The PMR spectra of selenophene, the isomeric 1-(selenien-2-yl)-3-phenylpropenones, and their thiophene analogs have been obtained.     

Synthesis of 2-amino-3-carbethoxy-4,5,6,7-tetrahydrobenzo[b]selenophene and some transformations based on it

A new method for the synthesis of 2-amino-3-carbethoxy-4,5,6,7-tetrahydrobenzo[b]selenophene was developed. The reaction of the latter with allyl isothiocyanate gave 2-(N-allylthioureido)-3-carbethoxy-4,5,6,7-tetrahydrobenzo[b]selenophene, which is cyclized to the potassium salt of 3-allyl-4-oxo-2-thio-3,4,5,6,7,8-hexahydrobenzo[b]selenopheno[2,3-d]pyrimidine on treatment with potassium hydroxide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 326–328, March, 1973.     

Chemistry of benzo[6-b]selenophene III. Selenoindoxyl derivatives

3-Acetoxybenzo[b]selenophene and its 2-methyl derivative, respectively, were synthesized by the cyclization of o-carboxyphenylselenoacetic and-(o-carboxyphenyl)selenopropionic acids. 3-Hydroxy-2,3-dihydrobenzo[b]selenophene and its 2-methyl derivatives were obtained by the reduction of selenoindoxyl and 2-methylselenoindoxyl with sodium borohydride. 3-Methyl-3-hydroxy-2,3-dihydrobenzo[b]selenophene was synthesized by the reaction of selenoindoxyl with methylmagnesium iodide.See [1] for communication II.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1640–1644, December, 1971.     

Synthesis of benzo[c]selenophene and derivatives via new routes

[reaction: see text] Benzo[c]selenophene has been generated via facile bromination-dehydrobromination as well as oxidation of the 1,3-dihydrobenzo[c]selenophene. Benzo[c]selenophene thus generated has been lithiated in situ and treated with ClCOOEt to give the first functionalized derivative subject to X-ray crystallographic analysis.     

Modulation of optical and electronic properties of quinoxailine‐based conjugated polymers for organic photovoltaic cells

The synthesis of donor–acceptor type semiconducting copolymers is described. Quinoxaline (QX) or difluorinated quinoxaline (DFQX) derivatives serve as electron acceptors, while thiophene (T) or selenophene (Se) serve as electron donors. Alternating polymers are synthesized through Stille cross‐coupling, and their thermal stability, optical and electrochemical properties, field‐effect carrier mobilities, film crystallinities, and photovoltaic performances are investigated. The intramolecular charge transfer between the electron‐donating and electron‐accepting units in the backbone induces absorption from 450 to 750 nm. The optical band‐gap energies of the polymers are between 1.65 and 1.73 eV, and depend on the polymer structure. Organic photovoltaic cells fabricated using a polymer composed of DFQX and selenophene (PSe‐DFQX) exhibit a power conversion efficiency of 5.14% with an open‐circuit voltage of 0.78 V, a short‐circuit current density of 11.71 mA/cm², and fill factor of 0.57 under AM 1.5 G irradiation (100 mW cm^?2). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1904–1914     

Un Nouveau type d'ouverture de sélénophénes condensés

A condensed selenophene ring can be opened by selenium-metal interconversion, when the selenium atom is α to a five-membered aromatic ring, as in selenopheno [2,3-b] thiophene. In tricyclic compounds bearing [2,3-b] condensed triophene and selenophene rings, the selenophene ring open, whether in central or in lateral positions. When the tricyclic compound bears two [2,3-b] condensed selenophene rings, only the central selenophene ring opens by interconversion. Corresponding [3,2-b]isomers do not undergo this ring opening.     

Cyclopenta[c]selenophene based cooligomers and their polymers: comparative study with thiophene analogues

Selenophene and thiophene capped cyclopenta[c]selenophenes were synthesized and characterized. Crystal structure determination of some representative compounds revealed that the substitution at 3,4-position in the form of cyclopentane ring of selenophene or thiophene does not make any significant twist in the trimer backbone, making the cooligomer nearly planar. All the cooligomers were electrochemically polymerized and compared with thiophene capped cyclopenta[c]thiophene polymer. DFT calculations predict that the cyclopentane substitution on the third repeating unit (and in general) of one dimensional polymer neither disturb the planarity nor causes any significant twist on the polymeric backbone unlike the 3,4-dialkyl substitution. The electrochemically prepared selenophene based polymers showed low band gap compared to that of thiophene analogues. Cyclopentane substitution on selenophene as well as thiophene makes the resulting polymer oxidatively more stable when compared to more familiar poly-ethylenedioxythiophene (PEDOT) or poly-ethylenedioxyselenophene (PEDOS) systems. Alternate polymers of cyclopenta[c]selenophenes (CPS)/cyclopenta[c]thiophene (CPT) and thiophene/selenophene possess the energy of HOMO and LUMO significantly lower than that of homopolymers of CPS and CPT, however, possess higher band gap than PCPS.