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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。
Dichloro-4,5-diazafluorene-9-one Palladium (Ⅱ) complex (PddafoCl_2) is a kind of macrocycle presents π-π stacking layered crystals. Its structure of the carbonyl function, with the nitrogenous nucleophile primary amine (RNH_2) to generate carbon-nitrogen-containing Schiff base derivatives. The ordered stacking structure of π-π stacking in the conjugated rings may produce semiconducting properties. However, there has been no report about the conductivity of Schiff base derivatives in the title system. Based on local density (LDA) functional theory and the first principle of pseudopotential plane wave method, the LDA / CA-PZ method in the CASTEP package of Materials Studio 4.0 was used to study the effects of dichloro-4,5-diazafluorene-9 - Ketopalladium complex and its Schiff base derivatives (where R ’= - CN, -COOH, -NO_2, -CHO, -CH_3, -CH_2CH_3) were studied. The results showed that this series system The energy gap between (1.082 6 ~ 1.622 2) eV and Fermi level intercept (7.5147 ~ 8.4538) electrch s · eV -1. Compared with dichloro-4,5-diazafluoren-9-one palladium complexes, the Schiff base derivatives with electron-withdrawing substituents attached significantly reduced the energy gap and enhanced the conductivity. Among them, Compound 2 has the smallest energy gap. Different Schiff base derivatives were constructed and the complexes showed different conductivity. With the R ’substituent group increased electronegativity, the conductivity of the system increased, this law in theory has theoretical guidance and prediction. Dichloro-4,5-diazafluorenone 9-ketone palladium (Ⅱ) and its Schiff base derivatives are expected to be widely used in different fields.