TY - JOUR

T1 - Bis(perfluoroaryl)chalcolanes ArF2Ch (Ch = S, Se, Te) as σ/π-Hole Donors for Supramolecular Applications Based on Noncovalent Bonding

AU - Рожков, Антон Викторович

AU - Жмыхова, Маргарита Владимировна

AU - Торубаев, Юрий Валентинович

AU - Катленок, Евгений Анатольевич

AU - Крюков, Дмитрий Михайлович

AU - Кукушкин, Вадим Юрьевич

PY - 2023/4/5

Y1 - 2023/4/5

N2 - Perfluorinated arenes (perfluoropyridine, perfluorotoluene, and perfluorobiphenyl) were converted to the bis(perfluoroaryl)chalcolanes ArF2Ch (Ch = S 59-88%, Se 54-84%, Te 10-41%) via the developed one-pot methodology. This method includes the generation of Na2Ch (formed in situ by the reduction of Ch with the system Na+[C10H8]·-) followed by its treatment with any one of the arenes. The crystal structures of (4-NC5F4)2S (2), (C12F9)2S (3) (p-CF3C6F4)2Se (4), (C12F9)2Se (6A,B; two polymorphs), (C12F9)2Te (9), and (4-NC5F4)2Te (8B; a novel polymorph) were determined by X-ray crystallography. In the solid state, compounds ArF2Ch are self-associated via σ-(Ch)-hole interactions with F (or N for 8B) and also π-π stacking between the arenes. The σ/π-hole donor properties of ArF2Ch were evaluated by molecular electrostatic potential surface analysis using the density functional theory approach. The maximum Vs(σ-hole) values (from +25 to +38 kcal/mol) increase in the order S < Se < Te along with an increase in the polarizability and decrease in the electronegativity of the Ch sites, while the π-hole depths (+14 to +20 kcal/mol) follow the opposite trend being the lowest for the TeII derivatives.

AB - Perfluorinated arenes (perfluoropyridine, perfluorotoluene, and perfluorobiphenyl) were converted to the bis(perfluoroaryl)chalcolanes ArF2Ch (Ch = S 59-88%, Se 54-84%, Te 10-41%) via the developed one-pot methodology. This method includes the generation of Na2Ch (formed in situ by the reduction of Ch with the system Na+[C10H8]·-) followed by its treatment with any one of the arenes. The crystal structures of (4-NC5F4)2S (2), (C12F9)2S (3) (p-CF3C6F4)2Se (4), (C12F9)2Se (6A,B; two polymorphs), (C12F9)2Te (9), and (4-NC5F4)2Te (8B; a novel polymorph) were determined by X-ray crystallography. In the solid state, compounds ArF2Ch are self-associated via σ-(Ch)-hole interactions with F (or N for 8B) and also π-π stacking between the arenes. The σ/π-hole donor properties of ArF2Ch were evaluated by molecular electrostatic potential surface analysis using the density functional theory approach. The maximum Vs(σ-hole) values (from +25 to +38 kcal/mol) increase in the order S < Se < Te along with an increase in the polarizability and decrease in the electronegativity of the Ch sites, while the π-hole depths (+14 to +20 kcal/mol) follow the opposite trend being the lowest for the TeII derivatives.

KW - перфторхалькоген

KW - халькогенная связь

UR - https://www.mendeley.com/catalogue/9ed3b4a1-301e-3390-84e6-1e1cc2983872/

U2 - 10.1021/acs.cgd.2c01454

DO - 10.1021/acs.cgd.2c01454

M3 - Article

VL - 23

SP - 2593−2601

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 4

ER -