Formation of a three-dimensional bispyridyl based metal-organic architecture containing unique Ag...Ag （d^10-d^10） interactions

A novel co-ordination polymer based on IB metal thiocyanates, [Ag2（NCS）2（4,4＇-bipy）]. （1）（4,4＇-bipy = 4,4＇-bispyridine）, has been synthesized by the pre-assembly method and characterized by X-ray crystallography. The complex exists as a three- dimensional network consisting of （AgSCN）. undulating layers linked by 4,4＇-bipy bridges.

具有膦配体的异核d^(10)-d^8配合物结构:Au-Pt配合物激发态性质的理论研究

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.