A new look at the chalcogen bond: π-hole-based chalcogen (Se, Te) bonding which does not include a σ-hole interaction

Abstract

The solid-state structures of co-crystals of chalcogenadiazoles (ChDAs) with the planar half-lantern PtII2 and mononuclear PtII complexes exhibit short Ch···PtII (Ch = Se, Te) contacts occurred between a metal site...

Dichotomy of π-stacking-directing noncovalent forces in organic–inorganic planar assemblies: the case of halo-substituted benzoquinones π-stacked with a platinum(ii) square-plane

“…1). In our previous studies, 44 we successfully used this complex as a chalcogen π-hole acceptor. It is stable toward oxidation ( e.g.…”

“…1). In our previous studies, 44 we successfully used this complex as a chalcogen π-hole acceptor. It is stable toward oxidation (e.g., by weak oxidizing agents such as QX; for relevant reports on their oxidation activity see ref.…”

“…Complex 1 was synthesized according to ref. 44. TGA measurements were performed with a NETZSCH TG 209 F1 Libra thermoanalyzer.…”

Te⋯I secondary-bonding interactions in crystals containing tellurium(ii), tellurium(iv) and iodide atoms: supramolecular aggregation patterns, nature of the non-covalent interactions and energy considerations

“…[27][28][29] In crystals of chalcogen-containing molecules, π-hole interactions can cooperate with σ-hole interactions [30][31][32] or even operate independently. 33,34 Instances of bifurcated [35][36][37] and charge-assisted 38,39 chalcogen bonds are also known. Computational chemistry calculations on the aforementioned neutral systems [31][32][33][34][35][36][37] and other non-charged systems 26,40 confirm that the energy imparted by the different interactions involving the tellurium are like or exceed those imparted by conventional hydrogen bonding.…”

Halide Complexes of 5,6‐Dicyano‐2,1,3‐Benzoselenadiazole with 1 : 4 Stoichiometry: Cooperativity between Chalcogen and Hydrogen Bonding

“…Due to this, the hole-based SBIs are highly directional. [1,35,[51][52][53][54][55][56][57][58][59][60][61][62] In SBIs with anions σ-holes are mainly involved. [35,59,[63][64][65][66] Orbital contribution into ChB aligns with the well-established Alcock model [1] as an overlap of guest anion's unshared n-MO with σ*-MO of the chalcogen-containing host accompanied by donation of the electron density (charge transfer-CT) from the guest onto the host, i. e., by their negative hyperconjugation.…”