Ligand engineering based on a closo-B_(12)-cage has been practiced in this work to design a series of stable gas-phase dianions[B_(12)(ECX)_(12)]^(2-)(E=N,P,and As;X=O,S,and Se)via ab initio calculations.The calculate...Ligand engineering based on a closo-B_(12)-cage has been practiced in this work to design a series of stable gas-phase dianions[B_(12)(ECX)_(12)]^(2-)(E=N,P,and As;X=O,S,and Se)via ab initio calculations.The calculated second electron affinities ranging from 1.2 to 3.4 eV indicate that these dianions are electronically stable against electron auto-detachment.Their electronic structures were analyzed based on molecular orbitals and natural bond orbitals.We found that in these designer dianions,the ECX ligands bind the B_(12)-cage via B-E covalent interactions.We simulated the photoelectron spectra of these dianions and discussed the potential application of[B_(12)(NCX)_(12)]^(2-)(X=O,S,and Se)salts as electrolytes in Li-or Mg-ion batteries.展开更多
基金support from the National Key Research and Development Program(Grant No.2019YFA0210600)the National Natural Science Foundation of China(22003048,U1866203,92066207)the Natural Science Foundation of Shaanxi Province(2021JLM-27,2020JZ-03).
文摘Ligand engineering based on a closo-B_(12)-cage has been practiced in this work to design a series of stable gas-phase dianions[B_(12)(ECX)_(12)]^(2-)(E=N,P,and As;X=O,S,and Se)via ab initio calculations.The calculated second electron affinities ranging from 1.2 to 3.4 eV indicate that these dianions are electronically stable against electron auto-detachment.Their electronic structures were analyzed based on molecular orbitals and natural bond orbitals.We found that in these designer dianions,the ECX ligands bind the B_(12)-cage via B-E covalent interactions.We simulated the photoelectron spectra of these dianions and discussed the potential application of[B_(12)(NCX)_(12)]^(2-)(X=O,S,and Se)salts as electrolytes in Li-or Mg-ion batteries.
