TY - JOUR

T1 - Chalcogen Bonding between Tellurium(II) and the Isocyanide Carbon

AU - Смирнов, Андрей Сергеевич

AU - Рожков, Антон Викторович

AU - Крюкова, Мария Александровна

AU - Суслонов, Виталий Валерьевич

AU - Иванов, Александр Юльевич

AU - Gomila, Rosa Maria

AU - Frontera, Antonio

AU - Кукушкин, Вадим Юрьевич

AU - Бокач, Надежда Арсеньевна

PY - 2024/11/24

Y1 - 2024/11/24

N2 - A novel type of chalcogen bond between tellurium(II) and the carbon atom of the isocyanide groups has been discovered in five cocrystals: 1·TePyF2 (two polymorphs), 2·TePyF2, 3·2TeTolF2, and 3·TePyF2. These were obtained by cocrystallization of monoisocyanide compounds CN-Np (Np-1 is 1-naphthyl; 1) and CNC6H4CCPh (2) and the bis-isocyanide 1,4-(CN)2C6Me4 (3) with the chalcolanes TePyF2 and TeTolF2 (PyF = 4-NC5F4, TolF = 4-CF3C6F4). The structures were studied by X-ray diffraction, revealing Te···C distances of 2.9-3.2 Å (77-85% of Bondi vdW sum) and also characterized by ATR FTIR spectroscopy. Computational analysis, including density functional theory (DFT) calculations, energy decomposition analysis (EDA), molecular electrostatic potential (MEP), quantum theory of atoms in molecules (QTAIM), noncovalent interaction (NCI) plot, and natural bond orbital (NBO) analysis, showed that these chalcogen bonds are primarily electrostatic but with relatively significant orbital contributions. Monofunctional acceptors (1 and 2) form di- and oligomers, while the bifunctional acceptor (3) creates extended supramolecular structures. Interaction strengths range from −6.4 to −9.6 kcal/mol for Te···CN contacts.

AB - A novel type of chalcogen bond between tellurium(II) and the carbon atom of the isocyanide groups has been discovered in five cocrystals: 1·TePyF2 (two polymorphs), 2·TePyF2, 3·2TeTolF2, and 3·TePyF2. These were obtained by cocrystallization of monoisocyanide compounds CN-Np (Np-1 is 1-naphthyl; 1) and CNC6H4CCPh (2) and the bis-isocyanide 1,4-(CN)2C6Me4 (3) with the chalcolanes TePyF2 and TeTolF2 (PyF = 4-NC5F4, TolF = 4-CF3C6F4). The structures were studied by X-ray diffraction, revealing Te···C distances of 2.9-3.2 Å (77-85% of Bondi vdW sum) and also characterized by ATR FTIR spectroscopy. Computational analysis, including density functional theory (DFT) calculations, energy decomposition analysis (EDA), molecular electrostatic potential (MEP), quantum theory of atoms in molecules (QTAIM), noncovalent interaction (NCI) plot, and natural bond orbital (NBO) analysis, showed that these chalcogen bonds are primarily electrostatic but with relatively significant orbital contributions. Monofunctional acceptors (1 and 2) form di- and oligomers, while the bifunctional acceptor (3) creates extended supramolecular structures. Interaction strengths range from −6.4 to −9.6 kcal/mol for Te···CN contacts.

KW - chalcogen bond

KW - noncovalent interactions

KW - isocyanide

UR - https://www.mendeley.com/catalogue/b92a5b5b-9489-3b5c-8779-3a3d7bf63d72/

U2 - 10.1021/acs.cgd.4c01351

DO - 10.1021/acs.cgd.4c01351

M3 - Article

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

ER -