Radicalradical chalcogen bonds: CSD analysis and DFT calculations.

Phys Chem Chem Phys

Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials and Chemical Engineering "Giulio Natta", Politecnico di Milano, Via L. Mancinelli 7, 20131 Milano, Italy.

Published: June 2020

This manuscript reports a combination of crystallographic analysis (Cambridge Structural Database) and theoretical DFT calculations in chalcogen bonding interactions involving radicals in both the Ch bond (ChB) donor and acceptor. As a radical ChB acceptor (nucleophile) we have used benzodithiazolyl radical (BDTA) and as Ch bond donors (electrophile) we have used dithiadiazolyl and diselenadiazolyl radicals of the general formula p-X-C6F4-CNChChN (Ch = S, and Se). We have evaluated how the para substituent (X) affects the interaction energy, spin density and charge/spin transfer from the electron rich BDTA radical to the electron poor dichalcogenadiazolyl ring. The ability of the latter rings to form ChBs in the solid state has been examined by a comprehensive search in the CSD; several cases are used to exemplify the preferred geometric features of the complexes and they are compared with the theory. The molecular surface electrostatic potentials calculated for these ChB donors allow for a very precise rationalization of the self-assembly motifs most frequently adopted in the crystalline state and of their relative robustness.

Download full-text PDF

Source
http://dx.doi.org/10.1039/d0cp01643hDOI Listing

Publication Analysis

Top Keywords

dft calculations
8
radicalradical chalcogen
4
chalcogen bonds
4
bonds csd
4
csd analysis
4
analysis dft
4
calculations manuscript
4
manuscript reports
4
reports combination
4
combination crystallographic
4

Similar Publications

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!