“Anti-electrostatic” halogen bonding in solution

Abstract

Halogen-bonded (XB) complexes between halide anions and a cyclopropenylium-based anionic XB donor were characterized in solution for the first time. Spontaneous formation of such complexes confirms that halogen bonding is...

Search for an exothermic halogen bond between anions

“…14,21,22,26,38,71–75 The imposition of a polarizable dielectric continuum as a model of solvation converts this dimer into a stable complex, lower in energy than the pair of separated ions. 12,23,24,28,36,37,40–45,76–78…”

“…30–35 Again, the Coulombic repulsions between ions of like charge can be successfully countered by attractive short-range forces and lead to a stable complex. The bulk of these findings pertain to halogen bonds 36–46 but there are recent studies beginning to emerge that indicate similar sorts of attractive anion–anion interactions apply to pnicogen bonds 47 and to those between systems such as AuCl 4 − pairs. 48 Our own group has been actively engaged in studies to test the boundaries of these ideas.…”

The Nitrogen Bond, or the Nitrogen-Centered Pnictogen Bond: The Covalently Bound Nitrogen Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

“…This is the case for interactions that are coulombic in origin (a positive site attracting a negative one [54, 80,95]). However, there are examples known in which anti-electrostatic interactions have been shown to occur [96,97], as well as instances where a positive site attracts a positive site [98], and a negative site attracts a negative site [51] when they are in close proximity. Although this has been suggested to be a consequence of electrostatic polarization [99][100][101][102][103], dispersion plays a significant role in stabilizing such interactions [25,89,98].…”

The Phosphorus Bond, or the Phosphorus-Centered Pnictogen Bond: The Covalently Bound Phosphorus Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

“…They are the result of attractive engagements between sites of unequal charge density and are often identified to be of Coulombic origin (a positive site attracting a negative one). Anti-electrostatic noncovalent interactions have been characterized recently [ 36 , 37 ]. Depending on the nature of the interacting units responsible for a molecular complex system, the extent of energy contributions due to repulsion (Pauli and electrostatic, resulting from like charges) acts against orbital interactions, polarization, and dispersion as attractive forces [ 36 ].…”