二氯-4,5-二氮芴-9-酮合钯(Ⅱ)及其席夫碱衍生物能带结构的理论研究  

Energy band structure calculation on dichloride-(4,5-diaza fluoren-9-one)palladium(Ⅱ) complex and its schiff's base derivatives

作　　者：许铭坚[1] 徐志广[1] 丘仕标[1] 何家贤[1] 

机构地区：[1]华南师范大学化学与环境学院,广东广州510006

出　　处：《计算机与应用化学》2011年第4期442-446,共5页Computers and Applied Chemistry

基　　金：广东省自然科学基金(8451063101000731)资助项目

摘　　要：二氯-4,5-二氮芴-9-酮合钯(Ⅱ)配合物(PddafoCl_2)是一类大环间呈现π-π堆积层状的晶体。其结构中的羰基官能团,可与含氮的亲核试剂伯胺(RNH_2)生成含碳氮席夫碱的衍生物。在共轭环间的π-π堆积下其有序的堆积结构可能产生具半导体性质,但对标题体系的席夫碱衍生物的导电性理论研究还未有见相关报道。基于局域密度(LDA)泛函理论,第一原理赝势平面波法,采用Materials Studio 4.0软件中的CASTEP程序包中的LDA/CA-PZ法研究二氯-4,5-二氮芴-9-酮合钯配合物及其席夫碱衍生物(其中R'=-CN、-COOH、-NO_2、-CHO、-CH_3、-CH_2CH_3)共7个体系的能带结构,结果表明该系列体系的能隙在(1.082 6～1.622 2)eV之间,Fermi能级上截距在(7.5147～8.4538)electrch s·eV^(-1)之间。与二氯-4,5-二氮芴-9-酮合钯配合物相比,连接吸电子取代基后的席夫碱衍生物,能隙明显缩少,导电性增强,其中以连接氰基的化合物2的能隙最小。构建不同的席夫碱衍生物,配合物呈现不同的导电性。随R'取代基团电负性增强,体系的导电性能增强,这一规律在实际应用中有理论指导和预测作用。二氯-4,5-二氮芴-9-酮合钯(Ⅱ)及它的席夫碱衍生物有望在不同的领域获得广泛的应用。Dichlorido（4,5-diazafluoren-9-one-N,N） Palladium（Ⅱ） complex（PddafoCl_2） is a macro cyclic crystal withπ-πstacking interaction.The structure of carbonyl functional groups could come into the Schiff base formation after reacting to a nitrogen-containing nucleophiles primary amine （RNH_2）.With theπ-πstacking interaction the crystal structure may has the semiconductor properties,but their electric property has few relevant theoretical calculation reports.Dichloride-（4,5-diazafluoren-9-one）-palladium（Ⅱ） complex and its Schiff＇s base derivatives（R＇ =-CN,-COOH,-NO_2, -CHO,-CH_3,-CH_2CH_3） were calculated to investigate energy band structure by using LDA/CA-PZ of CASTEP method program of Materials Studio4.0 which based on the density-functional（LDA） theory and a first-principles pseudo potential plane-wave method.Result shows that the length of forbidden band is between（1.0826 and 1.6222） eV,the density of states about Fermi level is between 7.5147 and 8.4538 electrons·eV^（-1）.Comparing title compound the length of forbidden band of its Schiffs base derivatives is significantly small with the attractive group,like N-cyano-9-（4,5- Diazafluoren） imine（2）,and this could enhance conductive properties.Various structure of Schiff base derivatives shows a different conductivity,and R＇ substituent with large electronegativity enhanced conductivity property.This rule has the role of theoretical guidance and forecast. Dichloride-（4,5-diazafluoren-9-one）-palladium（Ⅱ） complex and its Schiff＇s base derivatives may be widely in different fields of applications.

关 键 词：4 5-二氮芴-9-酮(Dafo) 席夫碱衍生物 密度泛函理论 能带结构 态密度 

分 类 号：TQ015.9[化学工程] TP391.9[自动化与计算机技术—计算机应用技术]