不对称双席夫碱过渡金属配合物的电子光谱和非线性光学性质的理论研究

本文采用密度泛函理论中的M05方法对比研究了一类双席夫碱及其衍生物与金属Co、Ni和Cu配位后配合物的结构,非线性光学性质以及激发态性质.结果表明,Co配合物的三重态,Ni配合物的二重态以及Cu配合物的单重态为最佳稳定结构.通过最佳稳定结构计算得到的配合物非线性光学性质表明,三种金属配合物中Cu配合物表现出较高的一阶和二阶超极化率.通过对其激发态性质分析表明在配体苯环上引入甲氧基使电子跃迁种类减少,导致超极化率下降,非线性光学性质减弱.     

不同溶剂中硝基苯胺分子非线性光学性质的研究

在含时密度泛函理论水平上研究了溶剂对硝基苯胺分子非线性光学性质的影响 .溶剂效应通过极化连续模型来研究 .首先采用极化连续模型在密度泛函理论水平上优化了硝基苯胺分子在溶剂中的几何结构 ,从而研究了溶剂引起硝基苯胺分子几何结构的变化 .然后采用极化连续模型在含时密度泛函理论水平上计算了不同溶剂中硝基苯胺分子的激发态能量和电偶极矩 ,并利用两态模型首次给出了不同溶剂中二次谐波振荡过程的一阶非线性超极化率的色散关系 .计算结果表明 ,极性溶剂对硝基苯胺分子的非线性光学性质有较大的影响 .在低的辐射场频率下 ,理论给出的一阶非线性超极化率的色散关系和实验结果符合得较好 .最后对所得结果从理论上给出了可能的解释并讨论了两态模型的可靠性 .     

有机分子第一超极化率色散效应和双光子共振增强理论研究

采用含时Hartree-Fock和多态求和方法计算了半花菁衍生物生色团的第一超极化率色散效应. 采用二能级模型研究了第一超极化率的双光子共振增强特征. 研究发现，第一激发态对半花菁非线性光学性质起决定性作用，随着入射光波长向短波方向移动，二次谐波产生β(-2ω;ω,ω)不断增大并且在950nm附近出现双光子共振效应，理论结果与实验结果较好相符. 此外，共振条件下的二能级模型需要考虑激发态弛豫效应. 研究结果为实验测量和实际应用提供了理论参考. 关键词： 分子非线性光学 超极化率 色散效应 共振增强     

一组Dawson型多金属氧酸盐和相应的有机-无机杂多化合物的超快非线性光学响应

通过时间分辨率为115fs的超快光克尔方法测量了多金属氧酸盐K8[P2Mo4W13M(H2O)O61] (M=Mn, Co, Ni, Cu, Zn)和相应的有机-无机杂多化合物(C19H25N2)7K3[P2Mo4W13MO62]在830nm处的三阶非线性光学性质。多金属氧酸盐阴离子和相应的杂多化合物都表现出很大的三阶非线性,其中M=Cu的取代物的非线性系数要比其他小一个数量级。通过比较有机-无机杂多化合物和生成前者的反应物的值,发现杂多化合物中的电荷转移效应极大的增强了三阶非线性光学性能。     

一组Dawson型多金属氧酸盐和相应的有机-无机杂多化合物的超快非线性光学响应(英文)

通过时间分辨率为115fs的超快光克尔方法测量了多金属氧酸盐K₈[P₂Mo₄W₁₃M（H₂O）O₆₁]（M=Mn,Co,Ni,Cu,Zn）和相应的有机-无机杂多化合物(C₁₉H₂₅N₂)₇K₃[P₂Mo₄W₁₃MO₆₂]在830 nm处的三阶非线性光学性质.多金属氧酸盐阴离子和相应的杂多化合物都表现出很大的三阶非线性,其中M=Cu的取代物的非线性系数要比其他小一个数量级.通过比较有机-无机杂多化合物和生成前者的反应物的γ值,发现杂多化合物中的电荷转移效应极大的增强了三阶非线性光学性能.     

一种新型金属配合物的非线性光学特性的研究

利用单光束Z扫描技术,在波长532nm、脉宽8ns的条件下研究了新型的金属有机配合物ECuCl2（BOEP）2]的三阶非线性光学性质。由实验结果发现配位化合物虽然没有明显的非线性吸收性质,但是其三阶非线性折射率比相应配体大很多。探讨了配合物的结构和其三阶非线性光学性质的关系,认为配位化合物的丌共轭离域体系的增大和金属中心离子与配体之间的电子转移是配合物具有更大非线性折射率的主要原因。选择具有π键的配体与金属离子合成为配合物,使其非线性效应明显增强,这对合成性能更好的非线性材料有一定的参考价值。     

几种新型金属配合物热致三阶非线性光学特性

利用连续激光Z-扫描方法研究了过渡金属Ni、Cu、Pd的新型有机配合物的热致三阶非线性光学特性。结果表明：在488nm和632．8nm波长连续激光激发下,这几种配合物的光学非线性折射主要来源于热效应。并由实验曲线计算了它们的热光系数dn／dT及热致非线性折射率n2。通过比较,发现热致非线性折射率与配合物分子结构、激发波长及在该波长下的线性吸收强弱有关。金属中心原子的原子序数越大,热光系数和折射率也相应的越大。在488nm波长激光激发下的dn／dT和n2大于该配合物在632．8nm波长激发下的dn／dT和n2,在同一波长下,化合物溶液在该波长下的吸收越强,其dn／dT和n2值也越大。     

过渡金属与氮共掺杂ZnO电子结构和光学性质的第一性原理研究

采用基于密度泛函理论框架下的第一性原理平面波超软赝势方法,结合广义梯度近似(GGA)研究了过渡族金属(Mn,Fe,Co,Cu)与N共掺杂ZnO的能带结构、电子态密度分布、差分电荷密度和光学性质.计算表明Mn，Fe，Co与N共掺ZnO的光学性质与Mn，Fe，Co单掺杂相近，但是过渡族金属与N共掺杂有利于获得p型ZnO. 关键词： ZnO 第一性原理 电子结构 光学性质     

取代基对8-羟基喹啉金属配合物电子光谱和二阶非线性光学性质的影响

在B3LYP/LANL2DZ/6-31G^*水平上优化目标化合物分子的几何结构,并分别在TD- B3LYP/LANL2DZ/6-31++G^**和B3LYP/LANL2DZ/6-31++G^**水平计算目标化合物分子的电子吸收光谱和二阶非线性光学性质.计算结果表明,引入共轭给电子基使配合物分子的最大吸收波长红移,强共轭吸电子基的引入使配合物的最大吸收波长蓝移,取代基的引入使IrQ₃型配合物的二阶非线性光学性质明显增大.对AgQ型配合物,电子跃迁属于配体内部的电荷转移（LLCT）.对PtQ₂和IrQ₃型配合物,电子跃迁属于LLCT和部分金属向配体的电荷转移.取代基对AgQ,PtQ₂,IrQ₃型配合物分子的跃迁性质几乎无影响. 关键词： 8-羟基喹啉金属配合物 电子光谱 二阶非线性光学性质 密度泛函理论     

密度泛函交换关联势与过渡金属化合物光学非线性的计算研究

在优化几何构型的基础上，对一系列强关联过渡金属化合物，采用密度泛函理论方法中各种 交换关联势计算了电子偶极矩、一阶光学极化率和一阶光学超极化率.考虑基组和频率影响 ，对比从头算MP2，HF方法及实验值，评价了各种交换关联势的计算表现.在此基础上，讨论 新的混合密度泛函交换关联势，以提高密度泛函理论方法计算含有过渡金属体系非线性光学 性质的精度. 关键词： 密度泛函方法 过渡金属化合物 非线性光学     

喹喔啉-2,3-二甲酰胺金属配合物的合成及光谱性质研究

本文首次合成了过渡金属Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）、Ｃ（Ⅱ）与喹啉－２,３－二甲酰胺形成的三种固体配合物。     

Spectro Analytical,Computational and In Vitro Biological Studies of Novel Substituted Quinolone Hydrazone and it’s Metal Complexes

Some novel transition metal [Cu (II), Ni (II) and Co (II)] complexes of nalidixic acid hydrazone have been prepared and characterized by employing spectro-analytical techniques viz: elemental analysis, ¹H-NMR, Mass, UV–Vis, IR, TGA-DTA, SEM-EDX, ESR and Spectrophotometry studies. The HyperChem 7.5 software was used for geometry optimization of title compound in its molecular and ionic forms. Quantum mechanical parameters, contour maps of highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO) and corresponding binding energy values were computed using semi empirical single point PM3 method. The stoichiometric equilibrium studies of metal complexes carried out spectrophotometrically using Job’s continuous variation and mole ratio methods inferred formation of 1:2 (ML₂) metal complexes in respective systems. The title compound and its metal complexes screened for antibacterial and antifungal properties, exemplified improved activity in metal complexes. The studies of nuclease activity for the cleavage of CT- DNA and MTT assay for in vitro cytotoxic properties involving metal complexes exhibited high activity. In addition, the DNA binding properties of Cu (II), Ni (II) and Co (II) complexes investigated by electronic absorption and fluorescence measurements revealed their good binding ability and commended agreement of K_b values obtained from both the techniques. Molecular docking studies were also performed to find the binding affinity of synthesized compounds with DNA (PDB ID: 1N37) and “Thymidine phosphorylase from E.coli” (PDB ID: 4EAF) protein targets.     

Quantum yield and photometric parameters of some transition metal ion schiff base complexes

In the present studies, a series of transition metal Ni(II), Mn(II), Co(II) and Cu(II) complexes were synthesized using a Schiff base ligand formed by condensation reaction of p-phenylenediamine with 2-hydroxy-1-naphthaldehyde. The prepared ligand and complexes were characterized by FTIR, HNMR, UV–Vis and fluorescence techniques. The peak in the HNMR spectra as well as important band in the FTIR spectra is discussed in relation to the molecular structure. Quantum yield of the prepared samples was calculated by taking quinine sulphate as a reference solvent. The quantum yield and fluorescence intensity of Ni(II), Mn(II) and Co(II) complexes were found to be more compared to Cu (II) complex and ligand. The photometric parameters were also calculated for ligand and complexes.     

Study on structure and properties of transition metal doped BiF3 by first-principles

Structure and physical properties of BiF₃ doped with M=Cr, Cu, Fe, Mn, Ni, Ti, V and Co are calculated by the DFT+U method. Effect of metal doping on the electronic structure and optical response of host materials BiF₃ is investigated systematically. New energy levels are formed and located within the band gap, which could decrease the recombination rate of e⁻/h⁺ pairs. Furthermore, transition metal doping extends the optical absorption of BiF₃ to the visible spectral region.     

Ni、Co/AAO纳米有序阵列复合结构光吸收特性的比较研究

在多孔阳极氧化铝(AAO)模板中分别沉积金属镍(Ni)、钴(Co),制备了Ni／AAO和Co／AAO纳米有序阵列复合结构,对其光吸收特性进行了比较研究。实验结果表明．相同结构参量的模板中,Ni、Co纳米粒子的表观形状随沉积时间的变化规律基本一致．但Co/AAO及Ni／AAO复合结构的光吸收特性却有较大差异。Ni／AAO复合结构表现出间接带隙半导体的光学特征．而Co／AAO复合结构具有直接带隙半导体的光学特征。同时,随金属沉积量的增加,Ni／AAO吸收边的红移量仅约为13nm．而Co/AAO复合结构的吸收边红移量却超过了80nm。用Maxwell-Garnett(M-G)理论分析了导致二者光吸收特性存在较大差异的主要原因。     

Examination of Polymeric Azomethine Compounds and Their Transition Metal Complexes by Using XRF and XRD Technique

In this study,the electronic transition properties and structural analysis of the metal complexes(Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ)and Mn(Ⅱ))of three different polymer ligands were performed by using XRF and X-ray diffraction(XRD)techniques,respectively.The structural analysis of the polymers and their complexes were performed by XRD technique and some of the polymers were found to be in the face-centred cubic(fcc)structure.In addition,the values of the present K X-ray intensity ratios are significantly greater than the values reported in literature.     

Synthesis,Thermal Behavior,and Antimicrobial Activity of a Novel Macrocycle and its Transition Metal Complexes Derived from Thiosemicarbazide

The present study reports the synthesis of Co(II), Ni(II), Mn(II), Cu(II), and Zn(II) complexes with a new macrocyclic ligand (L₂)- 1,2,8,9,11,14-hexaazacyclopentadeca-12,13-dioxo-10,15-dithione-2,7-diene. The macrocycle was derived from thiosemicabazone (L₁) and diethyloxalate that were prepared by the reaction of thiosemicarbazide and glutaraldehyde in the ratio of 2:1. The synthesized complexes and ligands were characterized by elemental analysis and molar conductance, magnetic susceptibility, ¹HNMR, IR, electronic, and thermogravimetric analyses. The molar conductance values confirmed that the Ni(II), Cu(II), Zn(II), Mn(II) and Co(II) complexes were 1:2 electrolytes. On the basis of electronic spectral studies and molar conductance measurements, the authors proposed an octahedral structure for Ni(II), Mn(II), and Co(II) complexes, tetrahedral geometry for Zn(II) complex, and square planar geometry for Cu(II) complex. The thermal behavior of the compounds was studied by TGA in a nitrogen atmosphere up to 750°C at the rate of 20°C/min. The TGA results revealed that the complexes had higher thermal stability than the macrocycle. All the synthesized compounds were screened against 4 bacteria (i.e., Streptococcus aureus, Escherichia coli, Bacillus subtillis, Salmonella typhimurium) and 2 fungi (i.e., Fusarium oryzae, Candida albicans). The results showed that the metal complexes inhibited the growth of bacteria to a greater extent as compared to the ligand.     

乙酰二茂铁缩肼基硫代甲酸苄酯镍/钴配合物现场红外光谱电化学研究

本文对非线性光学材料乙酰二茂铁缩肼基硫代甲酸苄酯 (HLSB)的镍 /钴配合物Ni(LSB) 2 /Co(LSB) 2进行了电化学和现场红外光谱电化学的比较研究 ,结果表明 ,平面型镍配合物桥联双二茂铁体系中的电子离域程度高 ,其氧化分为两步单电子可逆过程 ,分子内的两个二茂铁基之间存在着较强的电子交流 ,电子传递主要是通过配体的骨架链进行的 ,观察到出现在 1 4 53cm- 1 处的νCC 伸缩强振动峰。而变形四面体钴配合物桥联双二茂铁体系的氧化为一步两电子过程 ,分子中的电子离域程度低 ,抑制了两个二茂铁基之间的电子交流 ,两个二茂铁基近乎等同。