Maximal occupation by bases of π-hole bands surrounding linear molecules.

Abstract

Linear molecules such as CO2 contain a positive π-hole ring that surrounds C on the molecule's equator. Quantum calculations examine the question as to how many bases can simultaneously bind to this ring. Linear molecules examined are TO2 , where T=C, Si, Ge, Sn; bases are NCH and NH3 . CO2 engages in the weakest of the tetrel bonds, and can bind up to three NCH and two NH3 . Unlike σ-hole tetrel bonds, Si forms the strongest tetrel bonds, with interaction energies as high as 43 kcal/mol with NH3 . But like GeO2 , SiO2 can sustain only two bases in its equatorial ring. The π-hole ring of SnO2 can engage in up to four tetrel bonds with either NCH or NH3 , even though these bonds are weaker than those with GeO2 or SiO2 . As all of these complexes cast TO2 in the role of multiple electron acceptor, the resulting negative cooperativity makes each successive bond weaker than its predecessor as bases are added, as well as reducing the magnitude of the central molecule's π-hole.