8-羟基喹啉银(铂)金属配合物电子光谱与非线性光学性质

运用密度泛函理论B3LYP方法对8-羟基喹啉(银、铂)(AgQ、PtQ₂)金属配合物及其衍生物的非线性光学性质进行理论计算研究. 结果表明: 引入取代基使铂配合物的最强吸收波长产生较大红移. 最低能量跃迁吸收来自最高占据分子轨道(HOMO)到最低空分子轨道(LUMO)的d→π^*和π→π^*跃迁, 属于金属配体电荷转移(MLCT)与配体配体电荷转移(LLCT). 金属银和铂掺杂8-羟基喹啉使其三阶非线性光学系数γ值明显增大, 并且在配合物上引入―Ph, ―PhOCH₃, ―PhF₂, ―PhF₅基团将进一步增大γ值. 引入基团的供电子性越强, γ值增大的幅度越大, 引入基团的吸电子性越强, γ值增大的幅度越小.     

苯乙烯基-β-萘噻唑染料电子光谱的含时密度泛函研究

对苯乙烯基-β-萘噻唑染料系列用量子化学密度泛函方法(DFT)在B3LYP/6-31g水平上进行了几何构型全优化, 探讨了苯环对位上不同的取代基CH₃, OCH₃, N(CH₃)₂, 3,4-OCH₂O, NO₂等对分子电荷转移、前线轨道能量和电子光谱等性质的影响规律, 在此基础上采用含时密度泛函方法(TD-DFT)计算了分子第一激发态的电子跃迁能, 得到最大吸收波长λ_max. 计算结果表明, 上述5种取代基的引入, 均导致最大吸收波长红移. 与实验λ_max结果相比, 理论计算最大相对偏差为0.0501, 最小相对偏差为0.0085.     

环丙沙星-铜(Ⅱ)-TBZ/HPB配合物的合成、抗菌活性及与DNA作用

合成并表征了两个新的配合物：[Cu(HCP)(TBZ)](NO₃)₂·(H₂O)₂ (1)和[Cu(HCP)(HPB)](NO₃)₂·(H₂O)_1.5 (2)[HCP=环丙沙星,TBZ=2-(4′-噻唑基)苯并咪唑,HPB=2-(2-吡啶)-苯并咪唑]。配合物1属于三斜晶系,P1 空间群,a=0.909 5(2) nm,b=1.330 1(3) nm,c=1.355 2(3) nm,α=93.518(3)°,β=97.192(3)°,γ=106.361(3)°,V=1.552 6(6) nm³,Z=2,D_c=1.598 g·cm^-3,μ=0.849 mm^-1。用二倍稀释法研究了配合物的抗菌活性,发现配合物对大肠杆菌(Escherichia coli,G-)、沙门氏杆菌(Salmonella,G-)和枯草杆菌(Bacillus subtilis,G+)具有良好的抑制作用。应用电子吸收光谱、荧光光谱、粘度测定及凝胶电泳研究了配合物与DNA的作用,结果表明配合物以插入方式与DNA作用,在维生素C存在下通过·OH切割 pBR322 DNA双螺旋结构。     

氧化腈与丙炔1,3-偶极环加成反应中区域选择性的理论研究

用密度泛函(DFT)B3LYP/6-311＋＋G**方法研究了氧化腈(RCNO, R＝F, NO₂, OCH₃, OH, COOCH₃, CHO, CONH₂, H, CH₃)与丙炔的1,3-偶极环加成反应, 并且计算了不同温度下的反应速率常数, 讨论了氧化腈上不同取代基R的取代效应和温度对反应区域选择性的影响. 结果显示, 氧化腈与富电子亲偶极体——炔烃反应, 5-取代反应占优势; 氧化腈上取代基R为强吸电子基团时或在较高温度下, 有利于4-取代反应的进行.     

新型的含硫族元素碳硼烷配体的三(3，5-二甲基-1-吡唑)硼氢钼配合物的合成和分子结构(英)

三齿单核三(3，5-二甲基-1-吡唑)硼氢钼配合物Tp^*Mo(O)Cl₂ (1)(Tp^*=三(3，5-二甲基-1-吡唑)硼氢HB(C₃H(Me₂)N₂)₃)与含硫族元素碳硼烷的锂盐[(THF)₂LiE₂C₂B₁₀H₁₀(THF)]<     

手性3,5-二甲基-2-芳基-2-吗啉醇盐酸盐的合成及其晶体结构

以(S)-2-氨基丙醇为手性源与α-溴-3-氯苯丙酮反应, (R)-2-氨基丙醇为手性源与6-甲氧基-2-(2-溴丙酰基)萘反应, 分别合成了手性纯化合物(2R,3R,5S)-3,5-二甲基-2-(3-氯苯基)-2-吗啉醇盐酸盐(4a)和(2S,3S,5R)-3,5-二甲基-2-(6-甲氧基-2-萘基)-2-吗啉醇盐酸盐(4b), 利用X射线单晶衍射仪测定了两化合物的晶体结构和两化合物的空间结构, 并初步分析两化合物空间结构, 化合物4a晶体属正交晶系, 空间群为P2₁2₁2, 晶胞参数为: a＝0.8718(2) nm, b＝0.7883(2) nm, c＝2.0247(6) nm, Z＝4, V＝1.3915(7) nm³, D_c＝1.328 g/cm³, F(000)＝584, R₁＝0.0399, wR₂＝0.0797, S＝1.042. 化合物4b晶体属正交晶系, 空间群为P2₁2₁2₁, 晶胞参数为: a＝0.71035 (9) nm, b＝0.77703(10) nm, c＝2.9820(4) nm, Z＝4, V＝1.6318(4) nm³, D_c＝1.318 g/cm³, F(000)＝688, R₁＝0.0520, wR₂＝0.1108, S＝0.994.     

二(2-苯基-8-羟基喹啉)锌及其衍生物的电子光谱性质的含时密度泛函理论研究

采用从头算(ab initio)和密度泛函理论(DFT B3LYP)方法。对二(2-苯基-8-羟基喹啉)锌(Zn(qPh)₂)及其衍生物的基态结构进行优化，同时用ab initio HF单激发组态相互作用(CIS)法在6-31G基组上优化其最低激发单重态几何结构，用含时密度泛函理论(TD-DFT/B3LYP)及6-31G基组计算吸收和发射光谱。计算表明，该类物质电子在基态与激发态间的跃迁，主要是电子云分布由定域化向离域化的转变。吸收及发射光谱的计算值与实验值基本符合。该类化合物的电子亲和能较大，都是优良的电子传输材料，改变中心金属原子对配合物光谱性质影响不大。而羟基氧被硫原子取代后，化合物的吸收光谱产生明显红移。     

N，N′-双(2-吡啶甲基)二硫代草酰胺根桥联的三核铜(Ⅱ)配合物的合成及表征

Two new trinuclear copper(Ⅱ) complexes bridged with N,N′-Bis(2-pyridylmethyl)-Dithiooxamidate, ［Cu₃L₂］(ClO₄)₂(1) and ［Cu₃L₂］(NO₃)₂(2) (H₂L=N,N′-Bis(2-pyridylmethyl)-Dithiooxamide), have been synthesized, and characterized by elemental analyses, IR, UV-visible spectra, conductance and EPR spectra. The variable temperature magnetic susceptibility for complex (1) has been measured in the range of 1.5～298K. Experimental data of magnetic susceptibility are successfully fit to theoretical value based on the spin Hamiltonian operator: H=-2J(S₁S₂+S₂S₃)-2J′S₁S₃, S₁=S₂=S₃=1/2, giving the magnetic exchange parameters of 2J=-170 cm^-1 and 2J′=-7.2 cm^-1. This result indicates the presence of a strong antiferromagnetic spin exchange interaction between the Cu(Ⅱ) ions.     

调控从非手性双钯(Ⅱ)和双铂(Ⅱ)配位组装中心同非手性蒽基吡唑配体组装的配位分子角的超分子手性构筑

利用4-(4-(9-蒽基)苯基)-3, 5-二甲基-吡唑配体(L)与不同的双金属组装单元合成了一类新颖的配位分子角[M₂L₂]([(bpy)Pd]₂ L₂, 1; [(dmbpy)Pd]₂L₂, 2; [(phen)Pd]₂L₂, 3; [(ppy)Pt]₂L₂, 4, 其中bpy=2, 2′-联吡啶, dmbpy=4, 4′-二甲基-2, 2′-联吡啶, phen=1, 10-菲咯啉, ppy=2-苯基吡啶)。结果表明这类配位分子角是通过金属-金属成键作用与吡唑基团自发去质子的协同作用自组装形成。利用单晶X-射线衍射, ¹H和¹³C NMR, ESI-MS和荧光光谱等测试手段对配合物1~3的结构进行了测定。同时, 电中性的有机金属分子角[(ppy)Pt]₂L₂ (4)的结构也通过¹H和¹³C NMR, 质谱和荧光光谱等手段进行了表征。运用不同的非手性双金属组装中心同非手性配体L, 自组装得到的3个非手性配位分子角的晶体结构差别很大, 特别是由[(phen)Pd]₂组装中心形成的配位分子角3结晶得到了超分子手性构筑。     

调控从非手性双钯(Ⅱ)和双铂(Ⅱ)配位组装中心同非手性蒽基吡唑配体组装的配位分子角的超分子手性构筑

利用4-(4-(9-蒽基)苯基)-3, 5-二甲基-吡唑配体(L)与不同的双金属组装单元合成了一类新颖的配位分子角[M₂L₂]([(bpy)Pd]₂L₂, 1;[(dmbpy)Pd]₂L₂, 2;[(phen)Pd]₂L₂, 3;[(ppy)Pt]₂L₂, 4, 其中bpy=2, 2'-联吡啶, dmbpy=4, 4'-二甲基-2, 2'-联吡啶, phen=1, 10-菲咯啉, ppy=2-苯基吡啶)。结果表明这类配位分子角是通过金属-金属成键作用与吡唑基团自发去质子的协同作用自组装形成。利用单晶X-射线衍射, ¹H和¹³C NMR, ESI-MS和荧光光谱等测试手段对配合物1~3的结构进行了测定。同时, 电中性的有机金属分子角[(ppy)Pt]₂L₂ (4)的结构也通过¹H和¹³C NMR, 质谱和荧光光谱等手段进行了表征。运用不同的非手性双金属组装中心同非手性配体L, 自组装得到的3个非手性配位分子角的晶体结构差别很大, 特别是由[(phen)Pd]2组装中心形成的配位分子角3结晶得到了超分子手性构筑。     

Absorption and Fluorescence Emission Spectra of Molecules Containing Azo and/or Oxadiazole Units

The ground state structures of a series of organic molecules containing azo and/or oxadiazole units were obtained by means of density functional theory B3LYP/6-31G(d) method. The first singlet excited state structures were optimized by virtue of singlet-excitation configuration interaction CIS/6-31G(d) method. The absorption and fluorescence emission spectra were then evaluated via the time-dependent density functional theory B3LYP and PBE1PBE methods with 6-311++G(3df,2p) basis set. The calculation results show that compared with those of their parent molecules A-H, B-H, C-H, D-H, the absorption and emission wavelength values of all the derivatives show red shifts. The derivatives containing both the oxadiazole and methoxyl units are good candidates for longer absorption wavelength materials. The effects of azo, oxadiazole, and methoxyl units on the absorption and emission wavelength were discussed.     

8-巯基喹啉阴离子的锌配合物及其衍生物的电子光谱性质的含时密度泛函理论研究

采用从头算(ab initio)和密度泛函理论(DFT B3LYP)方法, 对配合物8-巯基喹啉锌Zn(tq)₂及其5种衍生物基态结构进行优化, 用含时密度泛函理论(TD-DFT/B3LYP)及6-31＋G(d)基组计算吸收光谱; 同时用ab initio HF 单激发组态相互作用(CIS)法在6-31G(d)基组上优化其最低激发单重态几何结构, 用含时密度泛函理论计算发射光谱. 结果表明, 电子在基态与激发态间的跃迁, 主要是在配体8-巯基喹啉(tq)环内的电荷转移, 电子从含S的苯硫酚环转移至含N的吡啶环上; 吸收光谱和发射光谱的计算值与实验值基本符合. 该类配合物都是优良的电子传输材料, 改变金属离子和取代基均可以调控发光材料的光谱波段.     

TD-DFT Study on the Electronic Spectrum Properties of 2,7＇-（Ethylene）- bis-8-hydroxyquinoline and Its Derivatives

The structures of 2,7＇-（ethylene）-bis-8-hydroxyquinoline and its derivatives were optimized at the ground states using ab initio HF and B3LYP methods. At the same time, the molecular structures of the first singlet excited state for 2,7＇-（ethylene）-bis-8-hydroxyqulnoline and its derivatives were optimized by CIS/6-31G（d）. The absorption and emission spectra based on the above structures were obtained by the time-dependent density functional theory （TD-DFT） by the B3LYP method with the 6-31G（d） basis set. The calculated results of luminescence originate from the electronic transition from the hydroxphenol ring of 8-hydroxyquinoline A to the pyridine ring of 8-hydroxyquinoline B. Their luminescence wave bands can be tuned by different substituents on the ligand of 8-hydroxyquinoline.     

TD-DFT Study on the Electronic Spectrum Properties of 2,7′-(Ethylene)-bis-8-hydroxyquinoline and Its Derivatives

The structures of 2,7′-(ethylene)-bis-8-hydroxyquinoline and its derivatives were optimized at the ground states using ab initio HF and B3LYP methods. At the same time, the molecular structures of the first singlet excited state for 2,7′-(ethylene)-bis-8-hydroxyquinoline and its derivatives were optimized by CIS/6-31G(d). The absorption and emission spectra based on the above structures were obtained by the time-dependent density functional theory (TD-DFT) by the B3LYP method with the 6-31G(d) basis set. The calculated results of luminescence originate from the electronic transition from the hydroxphenol ring of 8-hydroxyquinoline A to the pyridine ring of 8-hydroxyquinoline B. Their luminescence wave bands can be tuned by different substituents on the ligand of 8-hydroxyquinoline.     

6α和6β-羟基雄酮的电子光谱和核磁共振谱的理论研究

在B3LYP/6-31G(d)水平下,优化6α和6β-羟基雄酮的几何构型.用TD-B3LYP/6-31G(d)方法,计算它们的电子吸收光谱;采用规范不变原子轨道GIAO法,计算它们的1H-NMR和13C-NMR化学位移值.结果表明,6β-羟基雄酮比6α-羟基雄酮稳定;6α-羟基雄酮的最长吸收波长比6β-羟基雄酮的要长;6α和6β-羟基雄酮的部分原子的NMR值具有明显差别.     

ESIPT inspired fluorescent 2-(4-benzo[d]oxazol-2-yl)naphtho[1,2-d]oxazol-2-yl)phenol: experimental and DFT based approach to photophysical properties

ESIPT inspired fluorescent 2-(4-benzo[d]oxazol-2-yl)naphtho[1,2-d]oxazol-2-yl)phenol was synthesized from 1-amino-3-(1,3-benzoxazol-2-yl)naphthalen-2-ol. Photophysical behavior of the synthesized compound was studied using UV–visible and fluorescence spectroscopy in polar and non-polar solvents. The synthesized naphthoxazolyl benzoxazole is fluorescent and very sensitive to the micro-environment. It shows a single absorption and dual emission in non-polar solvents with large Stokes shift originating from Excited State Intramolecular Proton Transfer while in polar solvents only a single short wavelength emission is observed. Experimental absorption and emission wavelengths are in good agreement with those predicted using the Time-Dependent Density Functional Theory (TD-DFT) [B3LYP/6-31G(d)]. The largest wavelength difference between the experimental and computed absorption maxima was 16 nm (acetonitrile) and 7 nm (ethyl acetate, THF, and 1,4-dioxane) in the short and long wavelength regions, respectively. A largest difference of 25 nm was observed for the short wavelength emission in DMF and 22 nm for the longer wavelength emission in chloroform.     

Theoretical Studies on Electronic Spectrum Property of 2—（2—Hydroxyphenyl）pyridine Via Time—Dependence Density Functional Theory Method

The geometrical structures of 2-(2-hydorxyphenyl) pyridine(PP) and its protonation states were optimized by means of the B3LYP/6-31G(d) method.For all the selected systems,the existence of H-bond is in favor of the stability of the systems.On the basis of the optimized geometrical structures,their electronic spectrum properties were studied by time-dependent density functional theory(TD-DFT)methosd via a hybrid runction of B3LYP and 6-31G(d) basis set.The TD-DFT calculation result predicts the absorption spectrum of PP at 324nm (3.82eV),which is in very good agreement with the experimental value of 322nm (3.85eV)determined in solvent chloroform.The absorption spectra of the two protoation states both exert a red shift in various pH media.     

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．     

反式-双(二甲基苯膦)铂配合物二阶非线性光学性质的密度泛函理论研究

采用密度泛函理论B3LYP方法,在6-31G(d)的水平上对两种反式-双(二甲基苯膦)铂配合物的几何构型进行优化,在获得稳定构型基础上,利用TD-B3LYP方法得到体系的UV-Vis吸收光谱,并用有限场(FF/B3LYP)方法探讨体系的二阶非线性光学性质(NLO).结果表明,此类铂配合物具有较大的二阶极化率,以及在可见光范围内透明等优点,是具有很好应用前景的非线性光学材料.