论文部分内容阅读
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。
In order to reveal the effect of substituents on the electronic structure of ethynyl-bi-ferrocene propane, the density functional theory (DFT) method was used to simulate the effect of ethynylbisferrocene propane and its two derivatives, phenynylbisferrocene propane And the electron structure, frontier orbital, ionization energy (IP) and electron affinity (EA) of ferrocenyldithioferrocene propane, and the effects of substituents on the energy levels and energy gaps of the compounds were discussed. The calculated results show that the electron transition between ground state and excited state occurs mainly between bisferrocene propane and ethynylbenzene or ethynylferrocene. When the substituent is phenyl, the reduction of HOMO energy level is less than the decrease of LUMO energy level, so the overall energy gap between the two is reduced. When the substituent is ferrocene, the HOMO energy level increases and the LUMO energy level decreases, so that the HOMO-LUMO energy gap decreases. The maximal electron affinities of compound 6-phenynyl-bi-ferrocene propane and the smallest ionization energy of compound 6-ferrocene-propanediborferrocene were shown. It can be seen that phenyl group substituted alkynyl bisferrocene propane compound And the ferrocene-based substitution can enhance the hole transporting ability of the compounds, which makes the alkynyl bisferrocenyl propane compounds have better application prospect in the functional conductive materials.