TY - JOUR
T1 - Bis(perfluoroaryl)chalcolanes ArF2Ch (Ch = S, Se, Te) as σ/π-Hole Donors for Supramolecular Applications Based on Noncovalent Bonding
AU - Rozhkov, Anton V.
AU - Zhmykhova, Margarita V.
AU - Torubaev, Yury V.
AU - Katlenok, Eugene A.
AU - Kryukov, Dmitry M.
AU - Kukushkin, Vadim Yu
N1 - Funding Information:
The support of the Russian Science Foundation (Project 21-73-10030) is gratefully acknowledged. Physicochemical studies were performed at the Center for Magnetic Resonance, Center for X-ray Diffraction Studies, Thermogravimetric and Calorimetric Research Center and Center for Chemical Analysis and Materials Research, while theoretical calculations were performed at Computational Center (all belonging to Saint Petersburg State University). XRD equipment of shared experimental facilities of Kurnakov Institute of General and Inorganic Chemistry RAS was used for some X-ray structure determinations.
Publisher Copyright:
© 2023 American Chemical Society
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.
UR - http://www.scopus.com/inward/record.url?scp=85149711681&partnerID=8YFLogxK
U2 - 10.1021/acs.cgd.2c01454
DO - 10.1021/acs.cgd.2c01454
M3 - Article
AN - SCOPUS:85149711681
SN - 1528-7483
VL - 23
SP - 2593
EP - 2601
JO - Crystal Growth and Design
JF - Crystal Growth and Design
IS - 4
ER -