乙炔基双二茂铁丙烷衍生物的密度泛函理论研究

A density functional theory study of acetylene-diferrocenylpropane Derivatives

为揭示取代基对金属有机化合物乙炔基双二茂铁丙烷电子结构的影响,采用密度泛函理论方法模拟计算了乙炔基双二茂铁丙烷及其2个衍生物苯炔基双二茂铁丙烷及二茂铁炔基双二茂铁丙烷的电子结构、前线轨道、电离能(IP)以及电子亲和势(EA),并讨论了取代基对化合物能级和能隙的影响。计算结果表明,电子在基态与激发态间的跃迁,主要是发生在双二茂铁丙烷和乙炔基苯或乙炔基二茂铁之间。取代基为苯基时化合物最高占据轨道(HOMO)能级降低量小于最低空轨道(LUMO)能级降低量,因此二者之间的能隙总体降低。取代基为二茂铁基时化合物HOMO能级增加,LUMO能级降低,从而使HOMO-LUMO能隙降低。结合化合物6-苯炔基双二茂铁丙烷电子亲和势最大以及化合物6-二茂铁炔基双二茂铁丙烷电离能最小,可见苯基取代使炔基双二茂铁丙烷类化合物电子传输能力增强,而二茂铁基取代则可以使该类化合物的空穴传输能力增强,这使炔基双二茂铁丙烷类化合物在功能导电材料方面具有较好的应用前景。

The electronic structure, frontier molecular orbital and ionization power（IP）, electronic atTmities（EA） of compounds Fc-（CH3）2C-Fc＇-C-=CH （1）, Fc-（CH3）2C-Fc＇-C-=C-Ph （2） and Fc-（CH3）eC-Fc＇-C-=C-Fc （3） were calculated by using （DFT）B3LYP method. The influence of substitute on energy level and HOMO-LUMO energy gap of compounds was discussed. The calculated results indicate that the electronic transitions between the ground level and excited state are the electronic transitions from the difcrrocenyl propane unit to the enthylphenyl or enthylferrocenyl groups in molecules 2 and 3. The phenyl substituent unit decreases the HOMO energy and HOMO-LUMO energy gap, and increase EA; the ferrocenyl substituent unit increases the HOMO energy, decrease HOMO-LUMO energy gap and IP. Compounds 2 and 3 could be potentially used as electric materials.