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采用MP2和DFT方法优化一系列d10-d8配合物,[MM’(CN)2(PH2CH2PH2)2]+[M=AuI,M′=PtII(1),PdII(2),NiII(3);M’=PtII,M=AgI(4),CuI(5)]的基态结构,其中BH&H方法得到的金属间距离最接近相应的实验值.对于经典Au-Pt配合物:使用多种方法优化[AuPt(CN)2(PMe2CH2PMe2)2]+(1Me)的结构以验证取代基近似的合理性,采用单激发组态相互作用方法优化了1的两个低能三重激发态并且考查了环境效应(抗衡离子和溶剂分子)对其较低能激发态发射光谱的影响.计算结果显示1的两个低能三重激发态分别产生399和234nm发射,属于金属中心(Metal-centered,MC)跃迁和分子内电荷转移(Intramolecular Charge Transfer,ICT)的混合性质;由于电子激发到成键轨道,使得激发态金属间距离相对基态变短;环境效应使得较低能的MC/ICT激发态的发射光谱红移,如1·ClO的发射在473nm处,与实验测得[AuPt(CN)2(PCy2CH2PCy2)2]·ClO4的451nm固体发射相对应.
A series of d10-d8 complexes were optimized by MP2 and DFT. [MM ’(CN) 2 (PH2CH2PH2) 2] + [M = AuI, M’ = PtII (1), PdII (2) M ’= PtII, M = AgI (4), CuI (5)], in which the BH and H intermetallic distances are closest to the corresponding experimental values.For classical Au-Pt complexes: Structure of AuPt (CN) 2 (PMe2CH2PMe2) 2] + (1Me) To verify the rationality of substituent approximation, two low energy triplet excited states of 1 were optimized using a single excitation configuration interaction method and the environmental effects Ions and solvent molecules on their lower excited-state emission spectra.The calculated results show that the two low-energy triplet excited states of 1 generate 399 and 234 nm emission, respectively, belong to the metal-centered (MC) transition and intramolecular charge (ICT). Due to the electronic excitation to the bonding orbit, the distance between the excited metal and the ground state is shortened. The environmental effect makes the emission spectrum of the excited MC / ICT with lower energy to be red-shifted. For example, The emission of ClO at 473 nm corresponds to the experimentally measured 451 nm emission of [AuPt (CN) 2 (PCy2CH2PCy2) 2] .ClO4.