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Stability of B 12 (CN) 12 2− : Implications for Lithium and Magnesium Ion Batteries
Author(s) -
Zhao Hongmin,
Zhou Jian,
Jena Puru
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201600275
Subject(s) - ion , halogen , chemistry , lithium (medication) , fragmentation (computing) , electron , atomic physics , dissociation (chemistry) , binding energy , magnesium , ligand (biochemistry) , crystallography , physics , medicine , alkyl , organic chemistry , quantum mechanics , computer science , endocrinology , operating system , biochemistry , receptor
Multiply charged negative ions are seldom stable in the gas phase. Electrostatic repulsion leads either to autodetachment of electrons or fragmentation of the parent ion. With a binding energy of the second electron at 0.9 eV, B 12 H 12 2− is a classic example of a stable dianion. It is shown here that ligand substitution can lead to unusually stable multiply charged anions. For example, dodecacyanododecaborate, B 12 (CN) 12 2− , created by substituting H by CN is found to be highly stable with the second electron bound by 5.3 eV, which is six times larger than that in the B 12 H 12 2− . Equally important is the observation that CB 11 (CN) 12 2− , which contains one electron more than needed to satisfy the Wade‐Mingos rule, is also stable with its second electron bound by 1.1 eV, while CB 11 H 12 2− is unstable. The ability to stabilize multiply charged anions in the gas phase by ligand manipulation opens a new door for multiply charged species with potential applications as halogen‐free electrolytes in ion batteries.