The simple homodinuclear M-M single bonds for group II and XII elements are difficult to obtain as a result of the fulfilled s2electronic configurations,consequently,a dicationic prototype is often utilized to design ...The simple homodinuclear M-M single bonds for group II and XII elements are difficult to obtain as a result of the fulfilled s2electronic configurations,consequently,a dicationic prototype is often utilized to design the M^+-M^+single bond.Existing studies generally use sterically bulky organic ligands L^-to synthesize the compounds in the L^--M^+-M^+-L-manner.However,here we report the design of Mg-Mg and Zn-Zn single bonds in two ligandless clusters,Mg2B7-and Zn2B7-,using density functional theory methods.The global minima of both of the clusters are in the form of M2^2+(B7^3-),where the M-M single bonds are positioned above a quasi-planar hexagonal B7 moiety.Chemical bonding analyses further confirm the existence of Mg-Mg and Zn-Zn single bonds in these clusters,which are driven by the unusually stable B7^3-moiety that is bothσandπaromatic.Vertical detachment energies of Mg2B7-and Zn2B7-are calculated to be 2.79 e V and 2.94 e V,respectively,for the future comparisons with experimental data.展开更多
基金supported by the National Key R&D Program of China(No.2018YFE0115000)the Natural Science Foundation of Tianjin City(No.19JCYBJC19600)。
文摘The simple homodinuclear M-M single bonds for group II and XII elements are difficult to obtain as a result of the fulfilled s2electronic configurations,consequently,a dicationic prototype is often utilized to design the M^+-M^+single bond.Existing studies generally use sterically bulky organic ligands L^-to synthesize the compounds in the L^--M^+-M^+-L-manner.However,here we report the design of Mg-Mg and Zn-Zn single bonds in two ligandless clusters,Mg2B7-and Zn2B7-,using density functional theory methods.The global minima of both of the clusters are in the form of M2^2+(B7^3-),where the M-M single bonds are positioned above a quasi-planar hexagonal B7 moiety.Chemical bonding analyses further confirm the existence of Mg-Mg and Zn-Zn single bonds in these clusters,which are driven by the unusually stable B7^3-moiety that is bothσandπaromatic.Vertical detachment energies of Mg2B7-and Zn2B7-are calculated to be 2.79 e V and 2.94 e V,respectively,for the future comparisons with experimental data.
基金financially supported by the National Natural Science Foundation of China(No.52071276)the Natural Science Foundation of Chongqing City,China(No.cstc2020jcyj-msxm X0933)。
