TY - JOUR

T1 - Semicoordination Bond Breaking and Halogen Bond Making Change the Supramolecular Architecture of Metal-Containing Aggregates

AU - Zelenkov, Lev E.

AU - Ivanov, Daniil M.

AU - Sadykov, Evgeniy K.

AU - Bokach, Nadezhda A.

AU - Galmés, Bartomeu

AU - Frontera, Antonio

AU - Kukushkin, Vadim Yu

N1 - Funding Information: This work has been supported by the Russian Foundation for Basic Research (no. 20-03-00073). Physicochemical measurements were performed at the Center for XRD Studies (Saint Petersburg State University). V.Y.K. is grateful to South Ural State University (Act 211 Government of the Russian Federation, contract no. 02.A03.21.0011) for putting the facilities at his disposal. Financial support by MICIU/AEI of Spain (project no. CTQ2017-85821-R FEDER funds) is gratefully acknowledged. Publisher Copyright: © 2020 American Chemical Society. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/10/7

Y1 - 2020/10/7

N2 - The complex [Ni(S2COEt)2] (1) and 1,4-diiodotertafluorobenzene (1,4-FIB) or 1,3,5-triiodotrifluorobenzene (1,3,5-FIB) were cocrystallized to form solid adducts 1·2(1,4-FIB) and 1·2(1,3,5-FIB), respectively; the structures of the adducts were studied by X-ray crystallography. The introduction of any one of the FIBs dramatically changed the supramolecular architecture of 1, and the structure-directing interactions changed from predominantly Ni···S semicoordination (in 1) to I···S halogen bonding between an FIB and the electron-donating S atoms of 1 (in the adducts). The semicoordination bond breaking and halogen bond making upon the interaction of 1 with the FIBs make the employed crystal engineering approach relevant (or even similar) to the molecular synthesis of metal species. The DFT study indicates that the strength of both types of interactions in the adducts are comparable (-3.0 to -4.9 kcal/mol and -4.3 to -4.9 kcal/mol) but very different in regard to their physical nature. If the electrostatics determine the I···S halogen bonds, the Ni···S semicoordination bonding is basically dominated by orbital effects.

AB - The complex [Ni(S2COEt)2] (1) and 1,4-diiodotertafluorobenzene (1,4-FIB) or 1,3,5-triiodotrifluorobenzene (1,3,5-FIB) were cocrystallized to form solid adducts 1·2(1,4-FIB) and 1·2(1,3,5-FIB), respectively; the structures of the adducts were studied by X-ray crystallography. The introduction of any one of the FIBs dramatically changed the supramolecular architecture of 1, and the structure-directing interactions changed from predominantly Ni···S semicoordination (in 1) to I···S halogen bonding between an FIB and the electron-donating S atoms of 1 (in the adducts). The semicoordination bond breaking and halogen bond making upon the interaction of 1 with the FIBs make the employed crystal engineering approach relevant (or even similar) to the molecular synthesis of metal species. The DFT study indicates that the strength of both types of interactions in the adducts are comparable (-3.0 to -4.9 kcal/mol and -4.3 to -4.9 kcal/mol) but very different in regard to their physical nature. If the electrostatics determine the I···S halogen bonds, the Ni···S semicoordination bonding is basically dominated by orbital effects.

KW - NONCOVALENT INTERACTIONS

KW - COORDINATION CHEMISTRY

KW - ANAGOSTIC INTERACTIONS

KW - THIN-FILMS

KW - COMPLEXES

KW - METALLACYCLES

KW - PARAMETERS

KW - XANTHATES

KW - PROGRAM

KW - NICKEL

UR - http://www.scopus.com/inward/record.url?scp=85091592983&partnerID=8YFLogxK

U2 - 10.1021/acs.cgd.0c00999

DO - 10.1021/acs.cgd.0c00999

M3 - Article

AN - SCOPUS:85091592983

VL - 20

SP - 6956

EP - 6965

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 10

ER -