The Bifurcated σ-Hole···σ-Hole Stacking Interactions

Abstract

The bifurcated σ-hole···σ-hole stacking interactions between organosulfur molecules, which are key components of organic optical and electronic materials, were investigated by using a combined method of the Cambridge Structural Database search and quantum chemical calculation. Due to the geometric constraints, the binding energy of one bifurcated σ-hole···σ-hole stacking interaction is in general smaller than the sum of the binding energies of two free monofurcated σ-hole···σ-hole stacking interactions. The bifurcated σ-hole···σ-hole stacking interactions are still of the dispersion-dominated noncovalent interactions. However, in contrast to the linear monofurcated σ-hole···σ-hole stacking interaction, the contribution of the electrostatic energy to the total attractive interaction energy increases significantly and the dispersion component of the total attractive interaction energy decreases significantly for the bifurcated σ-hole···σ-hole stacking interaction. Another important finding of this study is that the low-cost spin-component scaled zeroth-order symmetry-adapted perturbation theory performs perfectly in the study of the bifurcated σ-hole···σ-hole stacking interactions. This work will provide valuable information for the design and synthesis of novel organic optical and electronic materials.

Various Sorts of Chalcogen Bonds Formed by an Aromatic System

“…One might thus approximate this 1 kcal/mol quantity as a reasonable estimate as to the S···S chalcogen bond strength when in this coplanar configuration. This value is quite similar to a computation at the much higher CCSD­(T) level with a complete basis set extrapolation. The monosubstituted SC 4 H 3 F dimer also engages in a perpendicular structure like that of b , which is primarily stabilized by a S···π ChB.…”

“…Nonetheless, dispersion appears to make the largest contribution to the interactions within structures d and e , as was also the case with the T-dimers. It is worth noting that the high proportion of dispersion in the coplanar structure, and the weaker but attractive electrostatic term, has been confirmed in earlier calculations of similar dimers extracted from X-ray structures. This similarity is of particular interest as the structures examined in this previous work had no possibility of H-bonds between the SC 4 ring units.…”

The Pnictogen Bond: The Covalently Bound Arsenic Atom in Molecular Entities in Crystals as a Pnictogen Bond Donor

“…There are relatively few reviews [ 3 , 18 , 19 , 20 , 21 , 22 ], original papers (for example [ 1 , 5 , 23 , 24 , 25 , 26 , 27 , 28 , 29 ]), overviews [ 30 ], and comments on the strength [ 31 ], nature [ 32 , 33 ], and propensity of elements of the pnictogen family (Group 15) to engage in pnictogen bonding [ 34 , 35 , 36 ]. The reason for this is probably because recent work on noncovalent interactions has focused largely on exploring σ-hole and π-hole interactions [ 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 ] associated with the main elements of the periodic table, with particular attention to the elements of Groups 14, 16, and 17, including hydrogen bonding [ 49 ].…”