TY - JOUR
T1 - Heterovalent chalcogen bonding
T2 - supramolecular assembly driven by the occurrence of a tellurium(ii)⋯Ch(i) (Ch = S, Se, Te) linkage
AU - Torubaev, Yury V.
AU - Rozhkov, Anton V.
AU - Skabitsky, Ivan V.
AU - Gomila, Rosa M.
AU - Frontera, Antonio
AU - Kukushkin, Vadim Yu
N1 - Funding Information:
This study is an integration of two diverse projects supported by the Russian Science Foundation (project 21-73-10030: synthetic experiments; project 19-13-00338: crystal engineering studies). The authors are grateful to the Center for X-ray Diffraction Studies, the Magnetic Resonance Research Center, the Center for Chemical Analysis and Materials Research, and the Thermogravimetric and Calorimetric Research Center (all belonging to Saint Petersburg State University) for the physicochemical studies. Part of the XRD experiments was performed using the shared facilities of the N.S. Kurnakov Institute of General and Inorganic Chemistry of RAS. The computational studies were funded by MICIU/AEI of Spain (project PID2020-115637GB-I00 FEDER funds).
Publisher Copyright:
© 2022 The Royal Society of Chemistry.
PY - 2022/9/5
Y1 - 2022/9/5
N2 - The dichalcogenides Ph2Ch2 (Ch = S, Se, Te) were cocrystallized with perfluorinated chalcogen bond donors TolF2Te and PyF2Te (TolF = 4-CF3C6F4, PyF = 4-NC5F4) to obtain the 1 : 1 cocrystals TolF2Te·Ph2Ch2 (Ch = S 1, Se 2, Te 3) and PyF2Te·Ph2Se2 (4). In the X-ray structures of 1-4, heterovalent TeII⋯ChI (Ch = S, Se, Te) chalcogen bonding was identified on consideration of the geometrical parameters and, in addition, based on the results of appropriate density functional theory (DFT) calculations including quantum theory of atoms-in-molecules (QTAIM), noncovalent interaction plot (NCIplot) analysis, molecular electrostatic potential surfaces (MEP), and atoms-in-molecules (AIM) charge analysis. The binding energy in the dimeric structure is in the range between −9.7 and −12.9 kcal mol−1, where the contribution of the heterovalent chalcogen bonding ranges from −4.7 to −6.5 kcal mol−1. In the TeII⋯ChI moiety, the TeII center plays the role of an electrophilic partner, while the chalcogens in the lower oxidation state, 1+, exhibit nucleophilic properties. The heterovalent TeII⋯ChI (Ch = Se, Te) chalcogen bonding was thus used for the targeted noncovalent integration of two Ch centers in different oxidation states.
AB - The dichalcogenides Ph2Ch2 (Ch = S, Se, Te) were cocrystallized with perfluorinated chalcogen bond donors TolF2Te and PyF2Te (TolF = 4-CF3C6F4, PyF = 4-NC5F4) to obtain the 1 : 1 cocrystals TolF2Te·Ph2Ch2 (Ch = S 1, Se 2, Te 3) and PyF2Te·Ph2Se2 (4). In the X-ray structures of 1-4, heterovalent TeII⋯ChI (Ch = S, Se, Te) chalcogen bonding was identified on consideration of the geometrical parameters and, in addition, based on the results of appropriate density functional theory (DFT) calculations including quantum theory of atoms-in-molecules (QTAIM), noncovalent interaction plot (NCIplot) analysis, molecular electrostatic potential surfaces (MEP), and atoms-in-molecules (AIM) charge analysis. The binding energy in the dimeric structure is in the range between −9.7 and −12.9 kcal mol−1, where the contribution of the heterovalent chalcogen bonding ranges from −4.7 to −6.5 kcal mol−1. In the TeII⋯ChI moiety, the TeII center plays the role of an electrophilic partner, while the chalcogens in the lower oxidation state, 1+, exhibit nucleophilic properties. The heterovalent TeII⋯ChI (Ch = Se, Te) chalcogen bonding was thus used for the targeted noncovalent integration of two Ch centers in different oxidation states.
UR - http://www.scopus.com/inward/record.url?scp=85139180657&partnerID=8YFLogxK
U2 - 10.1039/d2qi01420c
DO - 10.1039/d2qi01420c
M3 - Article
AN - SCOPUS:85139180657
SN - 2052-1545
VL - 9
SP - 5635
EP - 5644
JO - Inorganic Chemistry Frontiers
JF - Inorganic Chemistry Frontiers
IS - 21
ER -