[Pt2(P2O4H2)4]4-和[Pt2(P2O4CH4)4]4-基态和激发态性质的理论研究

采用从头计算MP2和CIS方法分别优化等电子双核d⁸配合物Pt₂(P₂O₄H₂)₄]^4-和Pt₂(P₂O₄CH₄)₄]^4-的基态和激发态结构。结果表明基态Pt-Pt距离分别为0.290 5和0.298 7 nm，与实验的0.292 5和0.298 0 nm符合。NBO计算的Pt-Pt键级以及Pt原子间伸缩振动说明Pt-Pt相互作用具有吸引本质。CIS计算揭示电子激发到Pt-Pt的σ(p_z)成键轨道使得相互作用增强。保持激发态几何，含时密度泛函理论(TD-DFT)计算的溶液发射分别为449和475 nm，与实验值512和510 nm接近。

Ground- and Excited-State Properties of [Pt2(P2O4H2)4]4- and [Pt2(P2O4CH4)4]4-: A Theoretical Study

Ab initio MP2 and CIS methods were employed to optimize the ground- and excited-state structures of Pt₂(P₂O₄H₂)₄]^4- and Pt₂(P₂O₄CH₄)₄]^4-, respectively, where the two structurally analogous complexes have an oxygen atom and a methylenic group in the ligand bridge. The Pt-Pt distances calculated in the ground state are 0.290 5 and 0.298 7 nm, which are in accordance with experimental values of 0.292 5 and 0.298 0 nm, respectively. The stretching vibration and bond order between the two Pt atoms indicate that the Pt-Pt interaction is attractive in nature. Upon excitation the Pt-Pt contraction trend is well reproduced in the CIS calculations. On the basis of the excited-state structures, TD-DFT achieved the result of the solution emissions at 449 and 475 nm, agreeing with experimental values of 512 and 510 nm, respectively.