2,4-二羟基苯乙酮缩异烟酰腙的实验和DFT理论研究:合成、晶体结构和性质及量化计算  

Experimental and DFT Studies of Pyridine-4-carboxylic Acid(2,4-dihydroxy-phenylethylidene)-hydrazide Schiff Base: Synthesis,Crystal Structure,Properties and Quantum Chemistry Calculation

作　　者：魏赞斌[1] 王金池[2] 江霞[3] 李颖茜 陈广慧[3] 解庆范[2] 

机构地区：[1]厦门大学化学与化工学院,福建厦门361005 [2]泉州师范学院化学与生命科学学院,福建泉州362000 [3]汕头大学理学院化学系,广东汕头515063

出　　处：《应用化学》2015年第9期1014-1021,共8页Chinese Journal of Applied Chemistry

基　　金：福建省教育厅A类重点项目(JA14261);国家级大学生创新创业训练计划项目(201410399017)~~

摘　　要：合成了一种酰腙类Schiff碱2,4-二羟基苯乙酮缩异烟酰腙(C14H13N3O3,H2L),经元素分析、红外光谱、紫外光谱、荧光光谱和热重分析等技术手段进行了表征。用X射线单晶衍射测定了它的晶体结构,该晶体属单斜晶系,C2/c空间群,晶胞参数a=2.0102(2)nm,b=0.75891(8)nm,c=1.9530(2)nm,α=90°,β=111.481(12)°,γ=90°,V=2.7725(5)nm3,Z=4,Dc=1.4292 g/cm3,R1=0.0422,wR2=0.1113,F(000)=1256。同时进行了量子化学计算研究。使用Gaussian09量子化学程序包,在密度泛函理论(DFT)的B3LYP/6-31G(d)水平,对化合物的分子结构进行全参数优化计算,获得了热力学参数和几何结构参数,对分子的总能量及前线分子轨道、Mulliken电荷分布进行了分析讨论;同时,用TD-DEF方法计算了化合物的电子吸收光谱和荧光发射光谱。A hydrazone-type Schiff base pyridine-4-carboxylic acid （2,4-dihydroxy-phenylethylidene）-hydrazide（H2L） was synthesized and characterized by elemental analysis, IR, UV, FL spectra, TGA and X-ray diffraction single crystal analysis which result showed that the crystal of HL·1.5H2O belongs to the monoclinic system, space group C2/c with cell parameters a=2.0102（2） nm, b=0.75891（8） nm, c=1.9530（2） nm, β=111.481（12）°, V=2.7725（5） nm^3, Z=4, Dc=1.4292 g/cm%3, R1=0.0422, wR2=0.1113, F（000）=1256. The compound formed 3-D supermolecule via intermolecular hydrogen bondings. The quantum chemical calculation was performed by means of Gaussian 09 program at B3LYP/6-31G（d） basis set.After optimization of molecular geometry, some important thermodynamic parameters and structural parameters were obtained. The molecular dipole moment, Wiberg bond order, Mulliken charge population and frontier molecular orbital energy have been analyzed and discussed. TD-DFT method is used to calculate the absorption and fluorescence spectra of the compound. CCDC 994067.

关 键 词：异烟酰腙 晶体结构 量子化学计算 光谱性质 热稳定性 

分 类 号：O625[理学—有机化学] O641[理学—化学]