TY - JOUR

T1 - Chalcogen bonds provide supramolecular association of beta-octamolybdate and chalconium cations

AU - Kuznetsova, Anna A.

AU - Yanshole, Vadim V.

AU - Il'in, Mikhail V.

AU - Novikov, Alexander S.

AU - Bolotin, Dmitrii S.

AU - Sokolov, Maxim N.

AU - Abramov, Pavel A.

N1 - Dmitrii S. Bolotin is grateful to the Saint Petersburg State University for financial support (grant number 103922061). Physicochemical studies were performed at the Center for Magnetic Resonance, Center for X-ray Diffraction Studies, and Center for Chemical Analysis and Materials Research (all at Saint Petersburg State University). Alexander S. Novikov is grateful to the RUDN University Scientific Projects Grant System (project no. 021342-2-000).

PY - 2024/11/20

Y1 - 2024/11/20

N2 - The interactions of triple σ-(QIV)-hole donating chalconium cations ([Q(bPh)R]+, when Q = S, Se, and Te) with nucleophilic beta-octamolybdate ([β-Mo8O26]4−) result in supramolecular association. The main focus of such assembly is on σ-(QIV)-hole recognition by the molybdate in cations with a biphenyl aromatic fragment. This leads to a remarkable diversity of the association patterns producing: (i) neutral 4 : 1 {[Q(bPh)R]4[β-Mo8O26]} complexes with cations stacked by π-π interactions; (ii) (Bu4N)+, [Q(bPh)R]+ and [β-Mo8O26]4− complexes of 2 : 2 : 1 stoichiometry with π-π interactions; (iii) (Bu4N)+, [Q(bPh)R]+ and [β-Mo8O26]4− complexes of a 2 : 2 : 1 stoichiometry without π-π interactions; and (iv) {[Q(bPh)R]2}2[β-Mo8O26] salts with π-π stacked cations but lacking any (QIV)⋯O interactions. Moreover, interactions in the system can drive the reorganization of [β-Mo8O26]4− into [α-Mo8O26]4−. The halogen-bonded (QIV)⋯O {(Q(bPh)R)x[β-Mo8O26]4−} (x = 2 and 4) assemblies, π-π stacked cationic dimers {(Q(bPh)R)2}2+ and complicated associates based on both types of interactions have been the subjects of crystallographic and computational studies.

AB - The interactions of triple σ-(QIV)-hole donating chalconium cations ([Q(bPh)R]+, when Q = S, Se, and Te) with nucleophilic beta-octamolybdate ([β-Mo8O26]4−) result in supramolecular association. The main focus of such assembly is on σ-(QIV)-hole recognition by the molybdate in cations with a biphenyl aromatic fragment. This leads to a remarkable diversity of the association patterns producing: (i) neutral 4 : 1 {[Q(bPh)R]4[β-Mo8O26]} complexes with cations stacked by π-π interactions; (ii) (Bu4N)+, [Q(bPh)R]+ and [β-Mo8O26]4− complexes of 2 : 2 : 1 stoichiometry with π-π interactions; (iii) (Bu4N)+, [Q(bPh)R]+ and [β-Mo8O26]4− complexes of a 2 : 2 : 1 stoichiometry without π-π interactions; and (iv) {[Q(bPh)R]2}2[β-Mo8O26] salts with π-π stacked cations but lacking any (QIV)⋯O interactions. Moreover, interactions in the system can drive the reorganization of [β-Mo8O26]4− into [α-Mo8O26]4−. The halogen-bonded (QIV)⋯O {(Q(bPh)R)x[β-Mo8O26]4−} (x = 2 and 4) assemblies, π-π stacked cationic dimers {(Q(bPh)R)2}2+ and complicated associates based on both types of interactions have been the subjects of crystallographic and computational studies.

UR - https://www.webofscience.com/wos/woscc/full-record/WOS:001353308200001

UR - https://www.mendeley.com/catalogue/72a21ac3-5665-3de0-962f-4e2b14e7b01e/

U2 - 10.1039/d4qi02258k

DO - 10.1039/d4qi02258k

M3 - Article

VL - 11

SP - 8902

EP - 8915

JO - Inorganic Chemistry Frontiers

JF - Inorganic Chemistry Frontiers

SN - 2052-1545

IS - 24

ER -