From weak to strong interactions: structural and electron topology analysis of the continuum from the supramolecular chalcogen bonding to covalent bonds

Abstract

The relation between covalent and supramolecular bonding, and the criteria of the assignments of different interactions were explored via the review of Se-and Te-containing structures in the Cambridge Structural Database...

Heterovalent chalcogen bonding: supramolecular assembly driven by the occurrence of a tellurium(ii)⋯Ch(i) (Ch = S, Se, Te) linkage

“…In the structures of 1-4, the intermolecular distances Te⋯Ch are significantly shorter than the sum of the corresponding recently revised Bondi vdW radii for chalcogens ( P vdW ðTe þ SÞ ¼ 4:19 Å, 6,52 P vdW ðTe þ SeÞ ¼ 4:28 Å, 6,52 and…”

“…Although chalcogen bonding (abbreviated as ChB)as part of a broad spectrum [1][2][3][4][5][6] of so-called "unorthodox" 7 or even "exotic" 8 noncovalent bondingwas only defined by IUPAC in 2019, 9 the physical nature of this phenomenon has been under study for several decades, initially within the framework of "secondary bonding" 10,11 or "hypervalency". 12,13 Since 2017, 14 at least one comprehensive analytical review of the general concept of ChB and applications of ChB in science and human physiology has appeared every year, 10,[14][15][16][17][18][19][20] and comparisons have been drawn between ChB and other relevant noncovalent interactions, such as hydrogen 10 and halogen bonding.…”

On the reliability of atoms in molecules, noncovalent index, and natural bond orbital to identify and quantify noncovalent bonds

“…28 In an alternate scheme, the energies of some of these bonds are sometimes assessed via a simple relationship with the potential energy density 24,[29][30][31] or other quantities extracted from AIM analysis. 24,27,[32][33][34] It would indeed be comforting for analysis of noncovalent bonds if the methods indicated above provided definitive indicators of the presence of such a bond, and if the data could be treated in a quantitative manner to compare strengths of such bonds. However, there have been numerous examples where the various methods conflict with one another as to which sorts of bonds might be present.…”

“…For example, it is common in the literature to consider the bond critical point density as a measure of bond strength 23–27 and possibly even with spectroscopic perturbations 28 . In an alternate scheme, the energies of some of these bonds are sometimes assessed via a simple relationship with the potential energy density 24,29–31 or other quantities extracted from AIM analysis 24,27,32–34 …”

Structure-Directing Interplay between Tetrel and Halogen Bonding in Co-Crystal of Lead(II) Diethyldithiocarbamate with Tetraiodoethylene

“…Non-covalent interactions [ 1 , 2 , 3 , 4 , 5 , 6 ] (NCIs) play a key role in the modulation of supramolecular organizations [ 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 ], which is useful for targeted crystal design [ 7 , 8 , 9 , 11 , 12 , 15 , 16 , 17 , 18 , 19 ] and the fabrication of functional materials [ 20 ], as well as for enhancing catalytic activity [ 21 , 22 ] and reactivity [ 23 , 24 , 25 , 26 , 27 , 28 ]. All of these factors contributed to the motivation behind supramolecular chemistry studies utilizing a diversity of NCIs.…”