3-(3’-吡啶基)-6-芳基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑衍生物基态和激发态性质

用密度泛函B3LYP方法对3-(3’-吡啶基)-6-芳基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑衍生物(芳基为苯基、3-吡啶基和苯乙烯基)进行基态几何构型全优化, 计算分子的电离势IP和电子亲和势EA等相关能量, 并用Zerner间略微分重叠(ZINDO)和含时密度泛函(TDDFT)方法计算吸收光谱, 用单组态相互作用方法(CIS)优化三种化合物分子的S1激发态结构, 分析其能量与发射光谱的关系, 计算溶剂中分子的吸收和发射光谱, 并与实验结果对照. 计算结果表明, 从3-(3’-吡啶基)-6-苯基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑分子(化合物A)到3-(3’-吡啶基)-6-(3’-吡啶基)-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑分子(化合物B)以及3-(3’-吡啶基)-6-对乙烯苯基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑分子(化合物C)的电子亲和势依次增大, 愈来愈容易接受电子, 吸收光谱和发射光谱红移.     

3-烷基/芳基-6-(3'-吡啶基)均三唑并[3, 4, -b]-1, 3, 4-噻二 唑类化合物的 合成

本文制备了一系列新的3-烷基/芳基-6-(3'-吡啶基)均三唑并[3,4-b]-1,3,4-噻二唑类稠杂环化合物,确认了结构,筛选了其中代表物的生物活性。     

电子传输材料噻二唑衍生物的密度泛函研究

用密度泛函B3LYP方法对7种3-(3'-吡啶基)-6-芳基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑分子进行全优化, 所有化合物都是平面分子. 计算了分子的垂直电子亲和势(VEA)、绝热电子亲和势(AEA)、分子内重组能以及绝对硬度等相关能量, 结果显示化合物的HOMO 与LUMO能级可通过连接不同取代基进行调节, 变化幅度为0.346～1.10 eV. 分子内重组能证实3-(4'-氰基-3'-吡啶基)-6-芳基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑是很有前途的电子传输材料, 不同取代基所对应的化合物分子内重组能也不同. 绝对硬度数据与分子内重组能都表明, 化合物E, G难于传输电子. 用TDDFT方法计算了化合物A, B和C的吸收光谱, 与实验值相比, 最大吸收峰的差值在3～10 nm之间.     

3-(4′-吡啶基)/苯基-6-芳基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑的合成及电化学性质表征

由化合物3-(4′-吡啶基)/苯基-4氨基-5-巯基-1,2,4-三唑与芳香酸在三氯氧磷作用下脱水、闭环得到3-(4′-吡啶基)/苯基-6-芳基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑类新型化合物,产率为42%~72%。该化合物具有较大的共轭平面,其结构经红外光谱、核磁共振氢谱、元素分析测试技术确证。电化学测试的工作窗口为-1.4~1.0V,负向扫描,循环伏安图中显示标题化合物均有还原峰,还原起始电位为-0.35~-0.95V。借鉴有机材料能带表征的方法,结合其紫外-可见光谱计算出了被测化合物的电子亲和势、电离势、带隙等电化学参数。结果表明,与常用的有机电子传输材料PBD相比,标题化合物具有较高的电子亲和势(3.79~4.39eV)和电离势(6.95~7.84eV),较高的电子亲和势有利于电子的传输。     

3-苯基-6-芳基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑的电子结构和光谱性质的含时密度泛函理论研究

对3-苯基-6-芳基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑(PATT)用量子化学密度泛函方法(DFT)在B3LYP/6-31G(d)水平上进行了几何构型的全优化, 探讨了分子电荷转移、前线轨道能量和电子光谱等性质的变化规律, 在此基础上采用含时密度泛函方法(TDDFT)计算了分子激发态的电子跃迁能. 将其与实验所得激发态的电子跃迁能结果相比, 理论计算最大相对偏差为0.071, 最小相对偏差为0.041.     

稠杂环化合物研究 i: 3-(4'-吡啶基)-6-芳基-均-三唑并[3,4-b]-1,3,4-噻二唑的合成及其抗菌性能

本文研究3-(4'-吡啶基)-4-氨基-5-巯基-1,2,4-三唑(1)与取代苯甲酸(2s-s)在氯化氧磷催化下的反应, 制得19种新的3-(4'-吡啶基)-6-芳基-均-三唑并[3,4-b]-1,3,4-噻二唑(3a-s), 确证了结构。初步观察了它们在约0.01%的浓度时, 对枯草杆菌, 大肠杆菌, 变形杆菌和金黄色葡萄球菌繁殖的抑制作用。     

稠杂环化合物研究 i: 3-(4'-吡啶基)-6-芳基-均-三唑并[3,4-b]-1,3,4-噻二唑的合成及其抗菌性能

本文研究3-(4'-吡啶基)-4-氨基-5-巯基-1,2,4-三唑(1)与取代苯甲酸(2s-s)在氯化氧磷催化下的反应, 制得19种新的3-(4'-吡啶基)-6-芳基-均-三唑并[3,4-b]-1,3,4-噻二唑(3a-s), 确证了结构。初步观察了它们在约0.01%的浓度时, 对枯草杆菌, 大肠杆菌, 变形杆菌和金黄色葡萄球菌繁殖的抑制作用。     

6-取代苄硫基-3-(3,4,5-三甲氧基苯基)-1,2,4-三唑[3,4-b][1,3,4]噻二唑类化合物的合成与抑菌活性

以4-氨基-5-(3,4,5-三甲氧基苯基)-3-巯基-1,2,4-三唑为原料,环化得到6-巯基-3-(3,4,5-三甲氧基苯基)-1,2,4-三唑[3,4-b][1,3,4]噻二唑再与取代苄氯反应,得到9个6-取代苄硫基-3-(3,4,5-三甲氧基苯基)-1,2,4-三唑[3,4-b][1,3,4]噻二唑类衍生物3a～3i.其结构经IR,1H NMR,MS和元素分析确证.初步生物活性测试结果表明部分化合物有一定的杀菌活性.     

稠杂环化合物的研究——Ⅵ.3-(3′-吡啶基)-6-脂肪基/芳香基均三唑并[3,4-b]-1,3,4-噻二唑的合成及生物活性研究

本文研究了3-(3′-吡啶基)-4-氨基-5-巯基-1,2,4-三唑在POCl_3存在下与脂肪酸和芳香酸的缩合反应,制得24种新的3-(3′-吡啶基)-6-脂肪基/芳基均三唑并[3,4-b]-1,3,4-噻二唑,利用元素分析、IR、~1H NMR及MS方法确认了结构。部分化合物进行了抗菌和除草试验。     

3, 6-二芳基-5, 6-二氢均三唑[3, 4-b][1, 3, 4]噻二唑的合成 及生物活性

研究了在L-(+)-酒石酸存在下3-芳基-4-氨基-5-巯基-1,2,4-均三唑与醛的Mannich反应及分子内的加成反应,合成了15个新的手性稠杂环化合物3,6-二芳基-5,6-二氢均三唑[3,4-b][1,3,4]噻二唑,利用IR、^1HNMR和MS确证了其结构,并测试了部分化合物的生物活性。     

7-氮杂吲哚衍生物分子基态和激发态性质的理论研究

用从头算HF和密度泛函B3LYP方法对7-氮杂吲哚衍生物1,3-二(N-7-氮杂吲哚基)苯、1,3,5 三(N-7-氮杂吲哚基)苯和4,4′-二(N-7-氮杂吲哚基)联苯进行全优化, 计算分子的电离势IP和电子亲和势EA等相关能量, 并用ZINDO和TDDFT方法计算吸收光谱, 用CIS优化三种化合物分子的S1激发态结构, 并分析其能量与发射光谱的关系, 计算溶剂中分子的吸收和发射光谱, 并与实验结果对照. 计算结果表明, 从7-氮杂吲哚到上述三种衍生物依次愈来愈容易接受空穴, 吸收和发射光谱红移.     

3,9-咔唑聚合物基态和激发态性质的理论研究

用密度泛函B3LYP方法对3,9-咔唑低聚物[(3,9-carbazole)n(n=1,2,3,4,6,8)]体系进行了全优化, 计算得到电离能、电子亲合势、空穴抽取能及电子抽取能等相关能量, 用ZINDO和TD-DFT方法计算得到吸收光谱; 分析了各种能量的变化及光谱规律. 用外推法由低聚物分子的各种性质与聚合度n相联系得到高聚物的性质, 将所得结果与2,7-咔唑(2,7-carbazole)及类似聚合物进行了比较分析. 结果表明, 3,9位聚合的咔唑整体共轭程度降低, 光谱蓝移, 其IP值和聚芴相近, 可以作为空穴接受材料应用于多层电子荧光器件的空穴传输层. 用CIS方法进行优化得到部分分子的S1激发态结构, 用ZINDO和TD-DFT方法得到对应的发射光谱.     

4-咔唑基-N-（3,′4′-二甲苯基）-1,8-萘二甲酰亚胺作为电子传输材料的实验和理论研究（英文）

通过乌尔曼偶联反应合成了一种新颖的萘胺-咔唑分子,4-咔唑基-N-（3,′4′-二甲苯基）-1,8-萘二甲酰亚胺（CNP）.运用量子化学中的密度泛函理论（TD-DFT）,在B3LYP/6-31（d）水平上对化合物在阴离子、阳离子、中性状态下进行了结构全优化,得到了化合物的总能量、HOMO能级、LUMO能级、电离能和电子亲合势.理论计算了化合物的紫外吸收光谱和红外光谱.紫外吸收光谱、红外光谱、HOMO能级和LUMO能级数值与实验值高度一致.在理论上分析了化合物作为电致发光材料的可能性,化合物CNP是一种很好的电子传输材料.     

Theoretical study on photophysical properties of multifunctional electroluminescent molecules with different pi-conjugated bridges

The photophysics of a series of molecular organic light-emitting diodes (OLEDs) has been studied by theoretical calculation. These molecular OLEDs have been integrated by an electron- and hole-transporting components as well as an emitting components into the donor-pi-acceptor (D-pi-A) structures: 2-carbazolyl-7-dimesitylboryl-9,9-diethylfluorene (1), trans-4'-N-carbazolyl-4-dimesitylborylstilbene (2), and trans-2-[(4'-N-carbazolyl)styryl]-5-dimesitylborylthiophene (3). To reveal the relationship between the structures and properties of these multifunctional electroluminescent materials, the ground- and excited-state geometries were optimized at the B3LYP/6-31G(d), HF/6-31G(d), and CIS/6-31G(d) levels, respectively. The ionization potentials and electron affinities were computed. The mobilities of hole and electron in these compounds were studied computationally based on the Marcus electron transfer theory. The lowest excitation energies (E(g)) and the maximum absorption and emission wavelengths of these compounds were calculated by time-dependent density functional theory methods. The solvent effect on the emission spectra of these compounds was considered by a polarizable continuum model. As a result of these calculations, it was concluded that the electron injections of these compounds are much easier than Mes(2)B[p-4,4'-biphenyl-NPh(1-naphthyl)], and the diethylfluorene-based compound has higher electron mobility and better equilibrium properties as compared to the stilbene-based and styrylthiophene-based compounds.     

Theoretical Study on the Optical Properties for 2,7- and 3,6-Linked Carbazole Trimers by Time-dependent Density Functional Theory

Electronic properties, such as HOMO and LUMO energies, band gaps, ionization potential (IP) and electron affinity (EA) of 2,7- and 3,6-linked carbazole trimers, two conjugated oligomers with different linkages of carbazole, were studied by the density functional theory with Becke-Lee-Young-Parr composite exchange correlation functional (B3LYP). The absorption spectra of these compounds were also investigated by time-dependent density functional theory (TD-DFT) with 6-31G* basis set. The calculated results indicated that the HOMO and LUMO of the 2,7- and 3,6-linked carbazole trimers are both slightly destabilized on going from methyl substitution to sec-butyl substitution. Both IP and EA exhibit their good hole-transporting but poor electron- accepting ability. The presence of alkyl groups on the nitrogen atoms does not affect the intra-chain electronic delocalization along the molecular frame. Thus no significant effect on the band gap and absorption spectra of compounds has been found.     

线型和星型平面噻吩类低聚物衍生物分子结构及光电性质研究

运用密度泛函DFT B3LYP／6-31G(d)方法对线型(a)和星型(b)平面噻吩类低聚物衍生物分别进行了几何构型优化,并采用含时密度泛函TD-DFT B3LYP／6-31G(d)方法计算了其紫外吸收光谱．计算结果表明:用TD-DFT．方法计算体系的紫外吸收光谱值与实验数据吻合;通过对噻吩类低聚物衍生物分子几何结构和前线分子轨道能级的分析,并从理论上解释了线型(a)和星型(b)衍生物光谱性质的差异:后者与前者相比较吸收光谱发生红移,这是由于星型结构使其相应HOMO能级升高,电离能(IP)降低,成为很好的电子给体和空穴传输材料．     

Experimental and theoretical study of three new benzothiazole-fused carbazole derivatives

Three new D-π-A type compounds, each containing one benzothiazole ring as an electron acceptor and one N-ethylcarbazole group as electron donor, were synthesized and characterized by elemental analysis, NMR, MS and thermogravimetric analysis. The absorption and emission spectra of three compounds were experimentally determined in several solvents and were simultaneously computed using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The calculated reorganization energy for hole and electron indicates that three compounds are in favor of hole transport than electron transport. The calculated absorption and emission wavelengths are well coincident with the measured data. The calculated lowest-lying absorption spectra can be mainly attributed to intramolecular charge transfer (ICT). And the calculated fluorescence spectra can be mainly described as originating from an excited state with intramolecular charge transfer (ICT) character. The results show that three compounds exhibited excellent thermal stability and high fluorescence quantum yields, indicating their potential applications as excellent optoelectronic material in optical field.     

Experimental and theoretical study of two new pyrazoline derivatives based on dibenzofuran

Two novel pyrazoline derivatives, named 2,8-bis(1,3-diphenyl-pyrazoline-5-yl)dibenzofuran (A) and 2,8-bis(1-(4-bromophenyl)-3-phenyl-pyrazoline-5-yl)dibenzofuran (B), were synthesized and characterized by elemental analysis, NMR, MS and thermogravimetric analysis. The absorption and emission spectra of them were determined by experimental methods in different polar solvents and were computed using the density functional theory (DFT) and the time-dependent density functional theory (TDDFT) at the same time. The calculated absorption and emission wavelengths are in good agreement with the experimental data. The fluorescence quantum yields and fluorescence lifetimes of them in different polar solvents were studied by means of steady state and time resolved fluorescence. The calculated reorganization energy for hole and electron indicates that the two compounds are in favor of hole transport than electron transport. The results show the two compounds present high fluorescence quantum yields and excellent thermal stability. It makes them of great interest as novel fluorescent probes and optoelectronic materials.