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, B12H122− 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, B12(CN)122−, 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 B12H122−. Equally important is the observation that CB11(CN)122−, 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 CB11H122− 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.
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, B12 H12 (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, B12 (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 B12 H12 (2-) . Equally important is the observation that CB11 (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 CB11 H12 (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.
The electronic structures of CuBO(2)(-), Cu(BO(2))(2)(-), Cu(2)(BO(2))(-), and Cu(2)(BO(2))(2)(-) clusters were investigated using photoelectron spectroscopy. The measured vertical and adiabatic detachment energies of these clusters revealed unusual properties of Cu(BO(2))(2) cluster. With an electron affinity of 5.07 eV which is larger than that of its BO(2) superhalogen (4.46 eV) building-block, Cu(BO(2))(2) can be classified as a hyperhalogen. Density functional theory based calculations were carried out to identify the ground state geometries and study the electronic structures of these clusters. Cu(BO(2)) and Cu(BO(2))(2) clusters were found to form chainlike structures in both neutral and anionic forms. Cu(2)(BO(2)) and Cu(2)(BO(2))(2) clusters, on the other hand, preferred a chainlike structure in the anionic form but a closed ringlike structure in the neutral form. Equally important, substantial differences between adiabatic detachment energies and electron affinities were found, demonstrating that correct interpretation of the experimental photoelectron spectroscopy data requires theoretical support not only in determining the ground state geometry of neutral and anionic clusters, but also in identifying their low lying isomers.
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