Spectroscopic Investigation of Chalcogen Bonding: Halide–Carbon Disulfide Complexes

Abstract

A combined experimental and theoretical approach has been used to study intermolecular chalcogen bonding. Specifically, the chalcogen bonding occurring between halide anions and CS2 molecules has been investigated using both anion photoelectron spectroscopy and high‐level CCSD(T) calculations. The relative strength of the chalcogen bond has been determined computationally using the complex dissociation energies as well as experimentally using the electron stabilisation energies. The anion complexes featured dissociation energies on the order of 47 kJ/mol to 37 kJ/mol, decreasing with increasing halide size. Additionally, the corresponding neutral complexes have been examined computationally, and show three loosely‐bound structural motifs and a molecular radical.

A tale of two conformers: spectroscopic evidence for halide catalysed formic acid isomerisation

“…The 2 P 3/2 photodetachment peak of iodide occurs at 3.06 eV, 32,33 when complexed with a carbon disulfide molecule this photodetachment peak shifts to 3.37 eV. 34 When complexed with a formaldehyde molecule, this photodetachment peak shifts further to 3.47 eV. 35 The relative size of the shift in energy associated with the photoeletron detachment serves as a proxy of binding strength, 34,36,37 allowing the conclusion to be drawn that the interaction with iodide is stronger with respect to formaldehyde compared with carbon disulfide.…”

Principles Guiding the Square Bonding Motif Containing a Pair of Chalcogen Bonds between Chalcogenadiazoles

“…In their most common divalent bonding pattern, each of the two R–Y bonds (Y = S, Se, and Te) engenders a separate σ-hole, thus setting up the possibility of two chalcogen bonds (ChBs). This sort of noncovalent bonding has been extensively studied in numerous contexts. − Trends emerging from these studies have shown that the ChB is progressively strengthened as the Y atom grows in size from S to Se to Te, and that the presence of electron-withdrawing substituents near the Y deepens the σ-hole and strengthens the ChB. These bonds have implications for numerous chemical and biological processes. − Among their numerous applications, ChBs can be utilized to construct certain sorts of synthons or triangular arrangements of appropriate molecules .…”

Chalcogen S∙∙∙S Bonding in Supramolecular Assemblies of Cadmium(II) Coordination Polymers with Pyridine-Based Ligands

“…Although not yet as established and studied as hydrogen and halogen bonding, chalcogen bonding (ChB) has recently gained more attention as an important supramolecular interaction with possible applications in biochemistry, crystal engineering, the design of new materials, and catalysis [1][2][3][4][5]. The chalcogen bond (D-Ch•••A) is a non-covalent interaction between a chalcogen bond donor D and a chalcogen bond acceptor A. Chalcogen bond donor D is a Lewis acid and acceptor A is a Lewis base, while Ch is a chalcogen atom (of group 16).…”

“…Nowadays, however, chalcogen bonds attract more attention, though their nature and mechanism of formation still remain unclear [1, 5,6]. In the case of the chalcogen bonds, the interactions are formed between a positive (electrophilic) region on the chalcogen atom and a negative electron density (nucleophilic region) on the chalcogen bond acceptor [1,4]. The anisotropy in the surface electrostatic potential on chalcogen atoms is crucial for the formation of chalcogen bonds, which become more evident when the radius of chalcogen atoms increases.…”

“…The strength of the chalcogen bonds seems to be dependent on the electron-accepting capability of the respective chalcogen molecule. Although understood from the crystal structures of various chalcogenated compounds for some time, the chalcogen bonds did not gain desired importance and become relevant supramolecular interactions in crystal engineering, in the way that halogen bonds did [4,6].…”