2,5-二[4-(2-芳基乙烯基)苯基]噁二唑的合成及发光特征

二乙烯联苯及其衍生物是一种可发射蓝光的小分子空穴型有机发光材料, 通过Wittig-Horner反应, 将电子传输型噁二唑环“嵌入”其中, 设计合成了6个2,5-二[4-(2-芳基乙烯基)苯基]-1,3,4-噁二唑化合物. 经光谱分析和元素分析等方法确认了它们的化学结构. IR和UV-vis分析数据表明标题化合物分子结构中的C＝C双键均为反式结构特征. 研究结果表明: 2,5-二[4-(2-对二甲氨基苯基乙烯基)苯基]-1,3,4-噁二唑具有良好的蓝色发光性能; 取代基对标题化合物的UV-vis吸收光谱和发光特性的影响显着.     

Poly(1,3,4-oxadiazole-imide)s containing dimethylsilane groups

New poly(1,3,4-oxadiazole-imide)s containing dimethylsilane units have been prepared by solution polycondensation reaction of an aromatic dianhydride incorporating dimethylsilane group, namely bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride, with different aromatic diamines having preformed 1,3,4-oxadiazole ring, such as 2,5-bis(p-aminophenyl)-1,3,4-oxadiazole, 2,5-bis[p-(4-aminophenoxy)phenyl]-1,3,4-oxadiazole, 2,5-bis[p-(3-aminophenoxy)phenyl]-1,3,4-oxadiazole, 2-(4-fluorophenyl)-5-(3,5-diaminophenyl)-1,3,4-oxadiazole, and 2-(4-dimethylaminophenyl)-5-(3,5-diaminophenyl)-1,3,4-oxadiazole. The polymers were easily soluble in polar organic solvents, such as N-methylpyrrolidinone, N,N-dimethylformamide, and pyridine, as well as in less polar organic solvents, such as tetrahydrofuran and chloroform. Very thin coatings deposited on silicon wafers exhibited smooth, pinhole-free surface in atomic force microscopy investigations. The polymers showed high thermal stability with decomposition temperature being above 415 °C.They exhibited a glass transition in the temperature range of 202-282 °C, with reasonable interval between glass transition and decomposition temperature. Solutions of the polymers in N,N-dimethylformamide exhibited fluorescence, having maximum emission wavelength in the range of 353-428 nm.     

对称4-枝和8-枝噁二唑衍生物的合成与荧光性质

采用Wittig-Horner和Heck反应合成了3个对称多枝[1,3,4]-噁二唑衍生物2,5-双{4-{4-[N,N-二(4-溴苯基)-氨基] 苯乙烯基}苯基}-1,3,4-噁二唑(BrPASPO), 2,5-双{4-{4-{N,N-二{4-{4-[5-(4-叔丁基苯基)-1,3,4-噁二唑基-2-]苯乙烯基}苯基}氨基}苯乙烯基}苯基}-1,3,4-噁二唑(TPASPO)和2,5-双{4-{4-{N,N-二{4-{3,5-二[5-(4-叔丁基苯基)-1,3,4-噁二唑基-2]-苯乙烯基}苯基}氨基}苯乙烯基}苯基}-1,3,4-噁二唑(OPASPO). 目标化合物的结构经过红外光谱、核磁共振氢谱、质谱和熔点确认. 在CH2Cl2溶液中三者的最大吸收波长分别在403 (BrPASPO), 408 (TPASPO)和409 nm (OPASPO), 荧光发射峰分别为495 (BrPASPO), 509 (TPASPO)和506 nm (OPASPO). 化合物TPASPO和OPASPO在CH2Cl2溶液中的荧光量子产率分别为0.47和0.45. 8枝化合物的荧光寿命高于4枝化合物. 对称多枝化合物具有很强的分子内电荷转移能力和荧光发射能力.     

Poly(1,3,4-oxadiazole-ether-imide)s and their polydimethylsiloxane-containing copolymers

Poly(1,3,4-oxadiazole-ether-imide)s were prepared by thermal imidization of poly(amic-acid) intermediates resulting from the solution polycondensation reaction of a bis(ether-anhydride), namely 2,2′-bis-[(3,4-dicarboxyphenoxy)phenyl]-1,4-phenylenediisopropylidene dianhydride, with different aromatic diamines containing 1,3,4-oxadiazole ring, such as 2,5-bis(p-aminophenyl)-1,3,4-oxadiazole, 2,5-bis[p-(4-aminophenoxy)phenyl]-1,3,4-oxadiazole, 2-(4-dimethylaminophenyl)-5-(3,5-diaminophenyl)-1,3,4-oxadiazole. Poly(1,3,4-oxadiazole-ether-imide)-polydimethylsiloxane copolymers were prepared by polycondensation reaction of the same bis(ether-anhydride) with equimolar quantities of an aromatic diamine having 1,3,4-oxadiazole ring and a bis(aminopropyl)polydimethylsiloxane oligomer of controlled molecular weight. A solution imidization procedure was used to convert quantitatively the poly(amic-acid) intermediates to the corresponding polyimides. All the polymers were easily soluble in polar organic solvents such as N-methylpyrrolidone and N,N-dimethylacetamide. The polymers showed good thermal stability with decomposition temperature being above 400 °C. Solutions of some polymers in N-methylpyrrolidone exhibited blue fluorescence, having maximum emission wavelength in the range of 370-412 nm.     

受体-给体-受体型双马来酰亚胺衍生物的合成及其荧光行为

对于含有给电子生色团的丙烯酰类单体和含有受电子生色团的乙烯氧基类单体的荧光行为以及光敏和光引发聚合行为 ,我们进行了长期系列的研究 [1～ 4 ] .含有给电子生色团的丙烯酰类单体可表示为A(=) - D(* ) 型单体 ,A(=) 表示受电子丙烯酰双键 ,D(* ) 表示给电子生色团 .反之 ,含有受电子生色团的乙烯氧基类单体可表示为 D(=) - A(* ) 型单体 ,D(=) 表示给电子乙烯氧基双键 ,A(* ) 表示受电子生色团 .在相同浓度下 ,这些单体的荧光强度总是远远低于其聚合物或相应饱和模型化合物的荧光强度 .为了区别于众所周知的浓度自猝灭 ,我们称这种…     

Light-emitting conjugated molecule containing 1,3,4-oxadiazole, carbazole and naphthalene units

A novel pi-conjugated small molecule VNCO, 2,5-bis{3'-[3'-vinyl-9'-(alpha-naphthyl)carbazolyl]phenyl}-1,3,4-oxadiazole, containing hole-transporting carbazole moieties, electron-injecting 1,3,4-oxadiazole moieties and chromophore naphthalene was designed and synthesized by Wittig reaction of 2,5-bis(3-tolylene-triphenylphosphonium bromide)-1,3,4-oxadiazole and 3-formyl-9-(alpha-naphthyl)carbazole. The UV-vis absorption, fluorescence excitation and emission spectra have been obtained in solution for VNCO. The photoluminescence (PL) of VNCO were examined in different solvents and the luminescence quantum yield was 0.746 in chloroform. It emitted blue and blue-green light, with the band gap of 3.30 eV estimated from the onset absorption. In addition, the light-emitting can be quenched by both electron donor (N,N-dimethylaniline) and electron acceptor (dimethylterephalate). Furthermore, the molecular interactions of VNCO with fullerene (C60) or carbon nanotubes (CNTs) were also carefully investigated.     

Electrospray ionization mass spectrometric study of 1,3,4-oxadiazole–copper complexes

The complexes of 2,5-disubstituted-1,3,4-oxadiazoles, namely 2,5-diphenyl-1,3,4-oxadiazole (1), 2,5-bis(2-pyridyl)-1,3,4-oxadiazole (2) and 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (3), with copper cation were studied by electrospray ionization mass spectrometry (ESI-MS). The ability of the compounds studied to form complexes with copper (under the ESI conditions) can be ordered as 2 > 1 > 3. The compounds studied tend to form both 1 : 1 and 2 : 1 chelate complexes with both copper(II) and copper(I). The complexes with copper(I) are formed in the ESI process. The influence of solvent polarity, solution flow-rate, counter ions (Cl⁻, NO₃⁻, CH₃COO⁻, SO₄²⁻, acetylacetonates) on the type of the ions observed was studied. Copyright © 2004 John Wiley & Sons, Ltd.     

Oxidative addition of N-aminophthalimide to 2-alkenyl-1,3,4-oxadiazoles. Synthesis of aziridinyloxadiazoles

Oxidation of N-aminophthalimide with lead tetraacetate in the presence of 2-[(E)-2-arylethenyl]-5-phenyl-1,3,4-oxadiazoles gives the corresponding 2-(3-aryl-1-phthalimidoaziridin-2-yl)-5-phenyl-1,3,4-oxadiazoles. From 2-phenyl-5-[(1E,3E)-4-phenylbuta-1,3-dien-1-yl]-1,3,4-oxadiazole only the addition product at both C=C bonds was obtained, while in the reaction with 2,5-bis[(E)-2-phenylethenyl]-1,3,4-oxadiazole both mono- and bis-adducts were isolated.     

Synthesis and Electrical Conductivities of Fully Conjugated Schiff Base Macrocycles Containing 1,3,4-Oxadiazole

Thedelocalizedrs-electronicplanarstructureofthemoleculeisnecessarytodesignneworganicmetals.Recentlymuchattentionwaspaidontheuseofmuchrigidelectronwithdrawingl,3.4-oxadiazoleunitasbuildingblocksinthesynthesisofsyntheticmetalsandorganiclight-emittingdiodesmaterials'-'.Previouslywehavefoundthecon.lugatedmacrocyclecontainingl,3,4-oxadiazolecouldbeoxidativelydopedwithiodinetoformacharge-transfercomplexwithaconductivityof4.6x10-'scm-'.Tocontinuethisworkandunderstandtherelationshipsbetweenmoleculars…     

Mass spectra of some perfluoroalkyl and perfluoroalkylether substituted 1,3,4-oxadiazoles

Electron impact fragmentation patterns were obtained for 2,5-bis-(perfluoroalkyl)-, 2,5-bis(perfluoroalkylether)-, and 2-perfluoroalkylether-5-perfluoroalkyl-1,3,4-oxadiazoles. All compounds gave parent ions. Cleavage β to the oxadiazole ring occurred preferentially; however, cleavage α to the ring also took place. Fragmentation of the ring was accompanied by the loss of a fragment of mass 28; this was most evident in the case of 2,5-bis(perfluoro-n-heptyl)-1,3,4-oxadiazole.     

含噁二唑单元共轭聚合物合成与性质研究

单体 2 ,5 双 (4 溴苯 ) 1,3,4 二唑 (M Ⅰ )与 1,4 二乙烯基 2 ,5 二正丁氧基苯 (M Ⅱ ) ,在钯催化下通过Heck偶合反应合成得到共轭聚合物 ;单体和聚合物进行了1 H NMR ,1 3C NMR、质谱、FT IR、UV、荧光光谱、GPC、元素分析、热分析等测试 ;二唑 (OXD)基团是一种很好的生色团 ,对氧和热特别稳定 ,二唑环的亲电子性能使其特别适合于作为电子传输层 ,聚合物能发射很强的绿色荧光 ,它将是一类潜在的光电高分子材料     

Crystal and molecular structure of 2,5-bis(fluorodinitromethyl)-1,3,4-oxadiazole

An X-ray structural study of 2,5-bis(fluorodinitromethyl)-1,3,4-oxadiazole (1), one of the representatives of azoles with strong electron-withdrawing substituents, has been carried out. It has been found that in the orthorhombic modification of1 the conformations of the fluorodinitromethyl groups are different. Intermolecular contacts in the crystal are realized through the heterocycles arranged at large angles to each other. The presence of strong electron-withdrawing substituents results in shortening of the C-O bonds and in a certain increase in the OCN angle in the 1,3,4-oxadiazole ring.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 639–641, April, 1994.     

Polynaphthylimides based on isomeric 2,5-bis[(aminophenoxy)phenylen]-1,3,4-oxadiazoles

Polynaphthylimides containing 1,3,4-oxadiazole cycles in main chains of macromolecules are prepared via the interaction of isomeric 2,5-bis[(aminophenoxy)phenyl]-1,3,4-oxadiazoles with dianhydrides of naphthalene-1,4,5,8-tetracarboxylic acid and 1,3-bis(1,8-dicarboxynaphthoyl-4)benzene. These polymers are synthesized through high-temperature polycyclocondensation in N-methylpyrrolidone and molten phenol. The relationships between the solubility and thermal characteristics of polynaphthylimides and their structure are studied, and the optical properties of the polymers are estimated.     

含1,3,4-噁二唑甲壳型液晶聚合物的合成与表征

甲壳型液晶聚合物（mesogen-jacketed liquid crystal polymer,MJLCP）是1987年由周其凤教授[1]首先提出的概念.从化学结构看,甲壳型液晶聚合物属于侧链型,由烯类单体经链式聚合制得,容易得到高分子量的产物,具有一般柔性侧链型液晶聚合物的一些优点.但是与柔性侧链型液晶聚合物不同的是,MJLCP分子中的刚性液晶基元是通过腰部或重心位置与主链相联结的,在主链与刚性液晶基元的侧基之间只有很短或者没有柔性间隔基.由于在这类液晶聚合物的分子主链周围空间内刚性液晶基元的密度很高,分子主链被由液晶基元形成的外壳所包裹并被迫采取相对伸直的刚性链构象.因此,这类液晶聚合物又和主链型刚性链液晶聚合物相似,具有较明显的链刚性.近年来,周其凤课题组围绕甲壳型液晶聚合物深入开展了分子设计与合成、分子结构与性能等多方面的研究.其中,设计合成具有特定功能的甲壳型液晶聚合物是在以往研究工作和学科交叉融合的基础上发展起来的一项新的研究工作.将一些有特殊功能的基团引入到甲壳型液晶聚合物中会使其具有崭新的特性.     

2,4和8-支噁二唑衍生物的三光子吸收和三光子上转换荧光

用飞秒Ti:sapphire激光测定了3个对称噁二唑衍生物4-{N,N-双[4-(4-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯乙烯基)苯基]氨基}苯甲醛(Bis-oxa)、2,5-双{4-[2-N,N-双(4-{4-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯乙烯基}苯基)氨基苯乙烯基]苯基}-1,3,4-噁二唑(Quadri-oxa)和2,5-双(4-{2-N,N-双[({3,5-二[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯基}乙烯基)苯基]氨基苯乙烯基}苯基)-1,3,4-噁二唑(Octu-oxa)的三光子吸收谱和三光子荧光光谱. 在1260 nm飞秒激光激发下, 2,4和8-支噁二唑衍生物的三光子吸收系数分别为5.0×10^-5, 10.0×10^-5和10.0×10^-5 cm³/GW², 三光子频率上转换荧光发射波长分别为533, 544和551 nm. 研究了多支化合物线性吸收和透过、单光子荧光及量子产率、荧光寿命、多光子荧光光谱和三光子吸收系数谱. 对称多支噁二唑衍生物具有很强的三光子吸收和上转换荧光性质.     

Synthesis, infrared and fluorescence spectra of lanthanide complexes with a new amide-based 1,3,4-oxadiazole derivative

A new amide-based 1,3,4-oxadiazole derivative ligand 2,5-bis[2-(N,N-diethyl-1'-oxopropylamide)phenyl]-1,3,4-oxadiazole (L) and its complexes, Ln(NO3)3L (Ln=La, Eu, Gd, Tb, Er), were synthesized. The complexes were characterized by elemental analysis, infrared spectra and conductivity. The lanthanide ions were coordinated by O atoms from CO. The fluorescence properties of Eu(NO3)3L and Tb(NO3)3L in the solid state and in different solvents were investigated. Under the excitation of UV light, these complexes exhibit characteristic fluorescence of europium and terbium ions. The solvent factors influencing the fluorescent intensity were discussed.     

Photochemistry of heterocyclic compounds—II : The photochemical reaction of 2,5-disubstituted 1,3,4-oxadiazoles with furan

The photochemical reaction of 2,5-disubstituted 1,3,4-oxadiazoles with furan has been studied. With or without benzophenone as a sensitizer, irradiation of 2,5-diphenyl-1,3,4-oxadiazole with furan in benzene solution gives the 1 : 1 cycloadduct, tetrahydrofuro[2·3-b]azetidino[2·1-b]-1,3,4-oxadiazole. However in the presence of iodine 3-acylfurans and their acylhydrazones are formed. A reaction pathway of this novel photo-induced acylation has been suggested.     

Spontaneously resolved chiral three-fold interpenetrating diamondoidlike Cu(II) coordination polymers with temperature-driven crystal-to-crystal transformation

The chiral 3-fold interpenetrating diamondoidlike Cu(II)-containing coordination polymer [Cu(2,5-bis(4-pyridyl)-1,3,4-oxadiazole)2(H2O)](ClO4)2]n (1a) is reported. It undergoes a temperature-driven reversible single-crystal-to-single-crystal structural transformation between room- (293 K, 1a) and low-temperature (150 K, 1b) forms.     

吡啶星型分子的双光子上转换荧光特性

用飞秒Ti:sapphire激光测定了一种星型吡啶分子2,5-二{4-{4-[N,N-二(4-吡啶乙烯基)苯基氨基]苯乙烯基}苯基}-1,3,4-噁二唑(PyPASPO)的双光子吸收截面及上转换荧光光谱.采用非线性透过率法测得二氯甲烷和四氢呋喃溶液中的其双光子吸收截面分别为412.5 和288.8 GM. 系统研究了吡啶星形分子PyPASPO的线性吸收和透过、单光子荧光、荧光寿命及激发-发射三维荧光谱和前线轨道能级. 在800 nm和150 fs钛宝石激光器激发下PyPASPO在二氯甲烷和四氢呋喃溶液中的双光子上转换荧光发射波长分别位于571和 525 nm,在二氯甲烷溶液中单光子荧光峰位于532 nm,荧光寿命为1.24 ns. HOMO和LUMO能级分别为-5.21 eV和-2.92 eV.增大分子内电荷转移有效增强了吡啶星形分子的双光子吸收和双光子上转换荧光发射能力     

侧链接有噁二唑的硅氧烷嵌段聚对苯乙烯撑衍生物的合成及其性能研究

在强碱条件下,单体2-(4-辛氧基苯基)-5-[4-(2,5-二溴甲基苯氧基)苯基]-1,3,4-噁二唑和二甲基二对溴甲基苯氧基硅烷发生Gilch脱卤聚合反应,成功合成了一种新型的侧链接有噁二唑的硅氧烷嵌段聚对苯乙烯撑衍生物(8),其结构经FT-IR表征。用UV-Vis,FL和DSC研究了8的光学性能和热稳定性。结果表明,8的热稳定性较单体有所改善;最大发射峰在480 nm。