二噻基苯和二噻基苯并噻二唑共聚物的固相合成

用相应的卤代芳烃与2-三丁基锡基噻吩在Pd(PPh3)4催化下合成了二噻基苯并噻二唑和二噻基苯两种噻吩类衍生物。在室温条件下,用无水FeCl3作为氧化剂,采用固相合成法制得了相应的共聚物。对所得的聚合物的形貌作了分析,并通过红外光谱、紫外-可见吸收光谱、荧光光谱等对所得聚合物的基本性能进行了表征。结果表明该共聚物在313nm和448nm处出现紫外吸收峰;在508nm处激发,在592nm处出现相应的荧光发射光谱。     

末端基为喹啉的1,4-二乙烯基苯衍生物的合成及光学性质研究

以1,4-二乙氧基苯为原料,通过氯甲基化反应和固相Wittig等反应,合成了一种末端基为喹啉的1,4-二乙烯基苯衍生物L:2,5-二乙氧基-1,4-二(2-喹啉乙烯基)苯,化合物结构经过IR,~1H NMR,~(13)C NMR,ESI-MS确证。测定了化合物在不同极性溶剂中的紫外-可见吸收光谱、荧光光谱及荧光量子产率;该化合物有两个吸收峰(分别在350 nm,410 nm附近),最大发射峰在480 nm附近;研究结果表明该化合物具有较好的光学性质。     

六苯并蔻类化合物的合成与性能研究

以四苯基环戊二烯酮和二苯乙炔衍生物为原料,在高温下(250~300℃)通过Diels-Alder加成反应合成了六苯基苯(HPB)和(4-溴苯基)五苯基苯(HPB—Br),进一步采用氯化铜和无水氯化铝为催化剂室温下在二硫化碳溶剂中脱氢环化获得标题化合物,并通过红外光谱、紫外-可见吸收光谱、核磁共振氢谱和元素分析对产物的结构进行了表征。热重分析表明,六苯并蔻类化合物具有较高的热稳定性;荧光光谱表明,六苯并蔻(HBC)和单溴代六苯并蔻(HBC—Br)的发光光谱都具有清晰的精细结构,最大发射峰位置分别在482.2和482.8nm处。     

2，6-二（2’-芳基-1’，3’，4’-噁二唑基）吡啶的合成与光谱性质

合成了3个2,6-二(2'-芳基-1',3',4'-(噁)二唑基)吡啶化合物,用1HNMR、FT-IR、MS对其结构进行了表征.研究了它,们的UV-Vis吸收光谱、荧光光谱.紫外.可见吸收光谱表明:目标化合物在278～309 nm出现最大吸收峰;荧光光谱表明:目标化合物在DMF溶液中发射强的紫色荧光,在364～398 nm出现最大发射峰;固体发射强的紫蓝色荧光,在376～414 nm出现最大发射峰.     

硼氟二吡咯亚甲基衍生物的合成、表征及光物理性质的研究

成功合成了中位为2-喹啉噻吩基硼氟二吡咯亚甲基和对葡萄糖四乙酸酯苯基的化合物4,4-二氟-8-[5'-(2-喹啉基)-2-噻吩基]-1,3,5,7-四甲基-4-硼-3a,4a-二氮杂-S-引达省和4,4-二氟-8-[4'-(2,3,4,6-O-四乙酰基-α-D-吡喃葡萄糖-1-氧基)苯基]-1,3,5,7-四甲基-4-硼-3a,4a-二氮杂-S-引达省,通过核磁进行表征。研究了这两个化合物在二氯甲烷中的紫外可见吸收光谱和荧光光谱,研究了化合物在薄膜和固体状态下的吸收光谱和荧光光谱,同时通过研究电化学性质得到化合物的HOMO和LUMO轨道。     

2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯的合成和非线性光学性质

报道了具有典型D-A-D型共轭结构的反式2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯(DCHO)的合成.用核磁、红外和元素分析进行了表征.测试了紫外吸收光谱、单光子荧光光谱、双光子荧光光谱及双光子吸收截面.在800 nm的飞秒脉冲激光激发下,标题化合物发出很强的绿色上转换荧光.化合物2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯的最大吸收波长、单光子发射波长、最大双光子荧光波长、荧光量子产率、双光子吸收系数及双光子吸收截面分别是393 nm、470 nm、475 nm、0.12、0.8 cm/GW、270 GM.这些数据表明,对位甲氧基的D-A-D型化合物具有较好的双光子吸收性能,DCHO是双光子荧光显微与成像应用的一个良好的候选材料.     

含噻吩环1,2,4-噁二唑类衍生物的合成及光电性能

以硫代二甘酸和取代苯甲腈为原料,经酯化、环化、酸化等反应合成了2,5-双[3-苯基-1,2,4-噁二唑-5-基]-3,4-二丁氧基噻吩衍生物,通过1HNMR、FTIR和元素分析进行了结构表征,并考察了该系列化合物的紫外-可见吸收光谱、荧光发射光谱及电化学性质。该系列化合物紫外吸收出现在240～250nm和320～350nm两个波段;荧光发射峰位于395～401.5nm,且随苯环上取代基供电子性的增强而规律性红移;循环伏安测定结果表明,该系列化合物中ⅧA、ⅧB、ⅧC和ⅧF具有高于常用电子传输材料2-(4-联苯基)-5-对叔丁基苯基-1,3,4-噁二唑(PBD)的电子亲和势,因而该类化合物的研究,对设计小分子类电致发光材料有重要意义。     

2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯的合成和非线性光学性质

报道了具有典型D-A-D型共轭结构的反式2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯(DCHO)的合成。用核磁、红外和元素分析进行了表征。测试了紫外吸收光谱、单光子荧光光谱、双光子荧光光谱及双光子吸收截面。在800 nm的飞秒脉冲激光激发下,标题化合物发出很强的绿色上转换荧光。化合物2,5-二氰基-1,4-二(4′-甲氧基苯乙烯基)苯的最大吸收波长、单光子发射波长、最大双光子荧光波长、荧光量子产率、双光子吸收系数及双光子吸收截面分别是393 nm、470 nm、475 nm、0.12、0.8 cm/GW、270 GM。这些数据表明,对位甲氧基的D-A-D型化合物具有较好的双光子吸收性能,DCHO是双光子荧光显微与成像应用的一个良好的候选材料。     

一种共轭炔基咔唑染料分子的合成及光谱性质研究

以二苯硫醚和咔唑为原料,合成了一种以碳碳三键作为桥接基团的新共轭炔基咔唑分子4,4'-二((N-乙基咔唑-3)-乙炔基)苯基硫醚(CZ-S-CZ),其结构经IR、~1HNMR和~(13)CNMR进行表征。通过紫外-可见吸收光谱研究表明,该物质在300~400 nm有较强的吸收。单光子荧光发射光谱研究表明,该化合物的单光子荧光最大发射波长是382 nm,荧光量子产率达到0.4。双光子激发荧光光谱研究表明,CZ-S-CZ在750~780 nm间具有双光子吸收性能,其双光子吸收截面最大可以达267.2 GM。     

二芳基乙烯类光致变色化合物的合成及其光电性质研究

在氮气及-78℃条件下,合成了两种二芳基乙烯类光致变色化合物1,2-双(2-甲基-5-(4-N,N-二甲氨基苯基)噻吩-3-基)全氟环戊烯(Ⅰa)和1,2-双(2-甲基-5-萘基噻吩-3-基)全氟环戊烯(Ⅱa),通过紫外-可见吸收光谱、荧光光谱、循环伏安法对其光谱特性和电化学性质进行了初步研究。在254nm紫外光照射下,Ⅰa和Ⅱa的氯仿溶液均由无色变为蓝色,最大吸收峰分别为620和570nm,在适当波长可见光照射下,均从有色态返回到无色态。通过UV-Vis光谱考察了这两种二芳基乙烯类化合物在溶液中的光致变色反应的动力学特征,实验结果表明,二芳基乙烯类光致变色化合物的闭环反应属于零级反应,开环反应为一级。电化学研究表明,在溶液中,Ⅰa和Ⅱa可发生不可逆的阳极氧化反应。     

A Novel and Expedient Approach to New Thiazoles, Thiazolo[3,2-a]pyridines, Dihydrothiophenes, and Hydrazones Incorporating Thieno[2,3-b]thiophene Moiety

This paper reports details about the synthesis of a series of novel functionalized symmetrical bis-heterocyclic compounds containing a thieno[2,3-b]thiophene motif. Bis-thiazole derivatives 2, 3a-c and thiazolo[3,2-a]pyridine derivatives 4a-c are achieved. The hitherto unknown dihydrothiophene derivatives 6a-dvia bis-pyridimium salt 5 are obtained. Additionally, the novel hydrazonothieno[2,3-b]thiophene derivatives 10a-c are obtained via bis-tosylacetylthieno[2,3-b]thiophene derivative 9. All compounds are characterized by (1)H-, (13)C-NMR, GCMS, IR, and UV-vis spectrometry. These compounds represent a new class of sulfur and nitrogen containing heterocycles that should also be of interest as new materials.     

两种卟啉化合物在Ag溶胶表面的紫外－可见吸收光谱和表面增强拉曼散射光谱研究

两种卟啉化合物在Ａｇ溶胶表面的紫外－可见吸收光谱和表面增强拉曼散射光谱研究王传义,刘春艳,阎晓斌,何建军,张曼华,沈涛（中国科学院感光化学研究,北京１００１０１）关键词卟啉,Ａｇ溶胶,表面增强拉曼光谱,紫外吸收光谱表面增强拉曼散射（ＳＥＲＳ）自１９７...     

Preparation and properties of new π-conjugated polyquinoxalines with aromatic fused rings in the side chain

Summary New π-conjugated polyquinoxalines with aromatic fused rings in their side chain have been prepared. Dehalogenative organometallic polycondensation of 5,8-dibromo[2,3-b]-acenaphthenequinoxaline and 5,8-dibromo[2,3-b]phenanthrenequinoxaline with a zerovalent nickel complex afforded poly([2,3-b]acenaphthenequinoxaline-5,8-diyl) (P(5,8-Qx(ace))) and poly([2,3-b]phenanthrenequinoxaline-5-8-diyl) (P(5,8-Qx(phen))) in high yields. P(5, 8-Qx(ace)) had an [η] value of 0.23 dL g⁻¹ and showed absorption and photoluminescence peaks at 445 and 565 nm, respectively. (P(5,8-Qx(phen))) gave absorption and photoluminescence peaks at 400 and 514 nm, respectively. XRD data indicated formation of ordered structures of the polymers in the solid. Preparation of related copolymer with thiophene is also reported. Received: 15 February 2000/Accepted: 2 March 2000     

The synthesis,optical properties and x-ray crystal structure of novel 1,3,4-oxadiazole derivatives carrying a thiophene unit

Novel, 1,3,4-oxadiazole derivatives carrying a thiophene unit were synthezised and their structures confirmed by elemental analysis, FT-IR and ¹H NMR. UV–vis absorption and photoluminescence spectroscopy revealed emission peaks located between 427 and 437 nm; the measured absorption λ_max and emission λ_em reflected the electron-donor character of the 1,3,4-oxadiazole derivatives. The crystal structure of one of the compounds was investigated.     

Perylene derivative sensitized multi-walled carbon nanotube thin film

Perylene-sensitized multi-walled carbon nanotubes (PV-MWNT) have been prepared by a π-stacking between nanotubes and perylene derivatives, N,N′-diphenyl glyoxaline-3,4,9,10-perylene tetracarboxylic acid diacidamide (PV). The resultant nanocomposites have been characterized by transmission electron microscope (TEM), UV-vis absorption, photoluminescence (PL) and photocurrent spectra. Long range ordering can be observed in the form of PV-MWNT via π-stacking by TEM. Red-shift in the optical spectra consisting of the UV-vis absorption and PL spectra with the attraction of PV on the surface of the MWNTs were observed. The evident quenching in PL spectra of PV-MWNT was ascribed to the absorption and transfer of recombination energy by MWNT. Photosensitivity spectra demonstrated an increasing photocurrent in the ultraviolet region and a broadening photosensitivity in the red spectral region for solar cells based on PV-MWNT.     

Defect-free Poly(9,9-bis(2-ethylhexyl)fluorene-2,7-vinylene) for Polymer Light-Emitting Diode (PLED) Devices

The π-conjugated light-emitting polymer poly(9,9-bis(2-ethylhexyl)fluorene-2,7-vinylene) (PEHFV), was synthesized in defect-free form via Horner-Emmons coupling. The structure and properties of the polymer were characterized by ¹H NMR, ¹³C NMR, UV-vis, photoluminescence (PL), and electroluminescence (EL) spectroscopies as well as gel permeation chromatography (GPC) and thermogravimetric analysis (TGA). The weight-average molecular weight (M_w) and polydispersity of the PEHFV were 34,000 g/mol and 2.3, respectively. The UV-vis spectra showed absorption maxima at 425 and 452 nm, and the PL emission spectra showed a maximum at 505 nm with a shoulder at 541 nm. The polymer was soluble in common organic solvents and easily spin-coated on indium-tin oxide (ITO)-coated glass substrates. A double-layer light-emitting device with an ITO/PEDOT:PSS/PFV/Al configuration was fabricated. The turn-on voltage for the PEHFV device was observed at 3.0 V.     

Photoluminescence of poly(thiophene) nanowires confined in porous anodic alumina membrane

Poly[3-(2-methoxyphenyl)thiophene] (PMP-Th) nanowires confined in the nano-channels of porous anodic alumina (PAA) membranes were first prepared through electrochemical deposition in cyclic voltammetry and investigated by photoluminescence (PL) spectroscopy. The morphologies and molecular structures of PMP-Th/PAA nanocomposites were studied with electron microscopy and FT-IR. The maximum absorption in UV–vis spectrum of the PMP-Th/PAA nanocomposites was located at 400–450 nm. The photoluminescence spectra show that the nanocomposites have green luminescence bands with the peaks at 560–570 nm. Compared to the electropolymerized PMP-Th film, the PMP-Th nanowires confined in the nano-channels of PAA membranes exhibit obvious blue-shifts in luminescent spectra and great enhancements in photoluminescence intensity. Further spectral analyses suggest that the PL enhancement could be attributed to Förster energy transfer from oxygen vacancies in PAA to PMP-Th molecules.     

The synthesis and photophysical properties of novel triphenylamine derivatives containing α, β-diarylacrylonitrile

α, β-Diarylacrylonitrile halides were prepared by condensation of appropriate arylaldehydes and arylacetonitrile halides using a catalytic amount of NaOCH₃ at room temperature. The diarylamines were reacted with various α, β-diarylacrylonitrile halides to afford several triphenylamine compounds, which displayed efficient hole transportation in the presence of Pd(OAc)₂/P(o-tolyl)₃ catalyst, thereby constituting organic light emitting device materials. The novel triphenylamine derivatives were characterized using FTIR, ¹H NMR, ¹³C NMR, MS and elemental analysis. The UV–vis absorption and photoluminescence spectra of the compounds were investigated. The lowest absorption band of α, β-diarylacrylonitrile-containing, triphenylamine derivatives, which occurred at ～400 nm, was assigned to charge-transfer transitions with an emission at 500–574 nm in different solutions and in the solid state.     

Electrosynthesis and characterization of poly(2-[(E)-2-azulen-1-ylvinyl] thiophene) using polyazulene as model compound

Electrochemical polymerization of azulene and 2-[(E)-2-azulen-1-ylvinyl] thiophene has been studied in this work. Characterization of the formed films was done by cyclic voltammetry (CV), in situ UV-vis absorption spectroscopy and by scanning electron microscopy (SEM). Polymerization was performed by CV in a three-electrode electrochemical cell in 0.1 M tetrabutylammonium hexafluorophosphate-acetonitrile (TBAPF₆-ACN) within two different potential ranges. The redox behavior of the films was studied by CV in monomer-free TBAPF₆-ACN electrolyte solution. The electrochemical response from the anodic charging (p-doping) in the different films consisted of symmetric and well-resolved redox peaks. During electrochemical doping changes in the UV-vis spectra can be seen due to transformation of the films from the neutral into the doped form. Poly(2-[(E)-2-azulen-1-ylvinyl] thiophene), in particular shows a very broad absorbance spectrum starting at 300 nm extending to 900 nm. Morphologies of the electrosynthesized films were studied by SEM.     

Comprehensive and Facile Synthesis of Some Functionalized Bis-Heterocyclic Compounds Containing a Thieno[2,3-b]thiophene Motif

A comprehensive and facile method for the synthesis of new functionalized bis-heterocyclic compounds containing a thieno[2,3-b]thiophene motif is described. The hitherto unknown bis-pyrazolothieno[2,3-b]thiophene derivatives 2a-c, bis-pyridazin othieno[2,3-b]thiophene derivatives 4, bis-pyridinothieno[2,3-b]thiophene derivatives 6a,b, and to an analogous bis-pyridinothieno[2,3-b]thiophene nitrile derivatives 7 are obtained. Additionally, the novel bis-pyradazinonothieno[2,3-b]thiophene derivatives 9, and nicotinic acid derivatives 10, 11 are obtained via bis-dienamide 8. The structures of all newly synthesized compounds have been elucidated by (1)H, (13)C NMR, GCMS, and IR spectrometry. These compounds represent a new class of sulfur and Nitrogen containing heterocycles that should also be of interest as new materials.