TY - JOUR

T1 - Metal-Bound Sulfur and Selenium Sites as Halogen Bond Acceptors: The Supramolecular Association of Rhodium(I) Half-Lantern Complexes with 1,4-Diiodotetrafluorobenzene

AU - Катленок, Евгений Анатольевич

AU - Байков, Сергей Валентинович

AU - Семенов, Артем Валерьевич

AU - Суслонов, Виталий Валерьевич

AU - Кукушкин, Вадим Юрьевич

PY - 2024/7/31

Y1 - 2024/7/31

N2 - The half-lantern Rh2I complexes trans-(Ch,N)-[Rh(μ-Ch∧N)(COD)]2 (Ch = S, Se; HCh∧N = 2-thiopyridine 1, 2-selenopyridine 2; COD = 1,5-cyclooctadiene) were cocrystallized with 1,4-diiodotetrafluorobenzene (1,4-FIB) to give isostructural cocrystals 1·1,4-FIB and 2·1,4-FIB, both studied by X-ray crystallography. The analysis of the structural data revealed a one-dimensional (1D) supramolecular arrangement, which is based on a poorly explored I···[Ch]-M halogen bonding. Density functional theory (DFT) calculations, using a set of complementary computational methods, closely interrogated these interactions and allowed the estimate of their energy (approximately −15 kcal/mol). In addition to the electrostatic and dispersion interaction components, the LP(Ch) → σ*(I-C) (LP = lone pair) charge transfer also noticeably contributes to the halogen bonding and provides some covalent character to this noncovalent interaction. The observed and studied assembly provides a route to supramolecular integration of metal-containing systems via ligand-involving halogen bonding, which include S or Se nucleophilic sites.

AB - The half-lantern Rh2I complexes trans-(Ch,N)-[Rh(μ-Ch∧N)(COD)]2 (Ch = S, Se; HCh∧N = 2-thiopyridine 1, 2-selenopyridine 2; COD = 1,5-cyclooctadiene) were cocrystallized with 1,4-diiodotetrafluorobenzene (1,4-FIB) to give isostructural cocrystals 1·1,4-FIB and 2·1,4-FIB, both studied by X-ray crystallography. The analysis of the structural data revealed a one-dimensional (1D) supramolecular arrangement, which is based on a poorly explored I···[Ch]-M halogen bonding. Density functional theory (DFT) calculations, using a set of complementary computational methods, closely interrogated these interactions and allowed the estimate of their energy (approximately −15 kcal/mol). In addition to the electrostatic and dispersion interaction components, the LP(Ch) → σ*(I-C) (LP = lone pair) charge transfer also noticeably contributes to the halogen bonding and provides some covalent character to this noncovalent interaction. The observed and studied assembly provides a route to supramolecular integration of metal-containing systems via ligand-involving halogen bonding, which include S or Se nucleophilic sites.

UR - https://pubs.acs.org/doi/10.1021/acs.cgd.4c00804

UR - https://www.mendeley.com/catalogue/01e9d590-6877-3bcf-8886-297c422ffc04/

U2 - 10.1021/acs.cgd.4c00804

DO - 10.1021/acs.cgd.4c00804

M3 - Article

VL - 24

SP - 6809

EP - 6818

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 16

ER -