Theoretical Study On The Structure, Metalophilic Interaction And Absorption Spectra Of Three-coordinated D¹⁰-d¹⁰ Metal Complexes

Metallophilic interaction is a hot topic in the field of organic metal and inorganic coordination chemistry.Many d10-d10 metal complexes containing metallophilic interaction have been widely used in the design of luminescent materials,magnetic materials,compression and conductive functional materials.Among them,d10-d10 metal complexes with phosphine as ligand are very popular because of their unique luminescent properties.Therefore,it is of great significance to study the structure,bonding and spectroscopic properties of d10-d10 metal complexes containing metallophilic interactions for the design and regulation of luminescent materials.In this paper,two kinds of d10-d10 netal complexes containing metallophilic interactions were designed theoretically.Their structures,metallophilic interactions and electron absorption spectra were studied by using MP2.density functional theory and chemical bond analysis.The main research contents are as follows:1.The structures,metallophilic interactions and electronic excitation energy of linear chains metal complexes PdmPtn[PH2(CH2PH)m+n-2CH2PH2]3(m+n=2-5)(1-18)have been investigated by using MP2 and density functional theory(DFT)methods.Calculated results indicated that geometries of PdmPtn(PH2CH2PH2)3(m+n=2)(1-3)optimized by SVWN5 method are well consistent with those by MP2 method and experiment.Then,SVWN5 functional was used to the investigation of the large system of PdmPtn[PH2(CH2PH)m+n-2CH2PH2]3 complexes.The lowest energy structures of complexes 1-18 optimized by SVWN5 method are singlet.Pd atoms in the mixed PdmPtn[PH2(CH2PH)m+n-2CH2PH2]3 complexes are favorable to locate at the ends of the metal chains.The interaction of Pd…Pd,Pd…Pt and Pt…Pt increases as the increase of m+n.The WBIs,AIM and RDG analysis indicates that the interactions between the adjacent transition metals belong to metallophilic interactions.The first electronic excitation energy of complexes 1-18 nonlinearly increases with m+n and follow the order of Pdm+n[PH2(CH2PH)m+n-2CH2PH2]3<PdmPtn[PH2(CH2PH)m+n-2CH2PH2]3<Ptm+n[PH2(CH2PH)m+n-2CH2PH2]3.2.In order to study the metallophilic interaction in completely overlapping and completely staggered metal complexes,the structure,metallophilic interactions and electronic excitation energy of phosphine ligand tri-coordination d10-d10 metal complexes[MM’(PH2CH2PH2)3]n+and[MM’(PH2C2H4PH2)3]n+(M,M’=Ag,Au,Pd and Pt)were studied theoretically.It is found that the bond length parameters obtained by SVWN5 functional optimization are in good agreement with the experimental results.The lowest energy structures of these complexes are singlet states.The distance between metals in[MM’(PH2CH2PH2)3]n+ and[MM’(PH2C2H4PH2)3]n+ with the same MM’ is shorter,indicating that the increase of carbon chain in the bridged ligand does not lead to the increase of the distance between metals,but to the shortening of the distance between metallophilic interaction.The WBIs,AIM and RDG analysis showed that the interaction between metals in these complexes was metallophilic.In addition,[MM’(PH2CH2PH2)3]n+ exhibit a red shift compared to that of[MM’(PH2C2H4PH2)3]n+(M,M’=Ag,Au,Pd and Pt)with the same MM’.