The interactions of tripleσ-(Q^(IV))-hole donating chalconium cations([Q(bPh)R]^(+),when Q=S,Se,and Te)with nucleophilic beta-octamolybdate([β-Mo_(8)O_(26)]^(4-))result in supramolecular association.The main focus o...The interactions of tripleσ-(Q^(IV))-hole donating chalconium cations([Q(bPh)R]^(+),when Q=S,Se,and Te)with nucleophilic beta-octamolybdate([β-Mo_(8)O_(26)]^(4-))result in supramolecular association.The main focus of such assembly is onσ-(Q^(IV))-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-Mo_(8)O_(26)]}complexes with cations stacked byπ-πinteractions;(ii)(Bu_(4)N)^(+),[Q(bPh)R]^(+)and[β-Mo_(8)O_(26)]^(4-)complexes of 2:2:1 stoichiometry withπ-πinteractions;(iii)(Bu4N)+,[Q(bPh)R]+and[β-Mo_(8)O_(26)]^(4-)complexes of a 2:2:1 stoichiometry withoutπ-πinteractions;and(iv){[Q(bPh)R]_(2)}_(2)[β-Mo_(8)O_(26)]salts withπ-πstacked cations but lacking any(Q^(IV))…O interactions.Moreover,interactions in the system can drive the reorganization of[β-Mo_(8)O_(26)]4-into[α-Mo_(8)O_(26)]^(4-).The halogen-bonded(Q^(IV))…O{(Q(bPh)R)_(x)[β-Mo_(8)O_(26)]^(4-)}(x=2 and 4)assemblies,π-πstacked 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.展开更多
基金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)the RUDN University Scientific Projects Grant System(project no.021342-2-000).
文摘The interactions of tripleσ-(Q^(IV))-hole donating chalconium cations([Q(bPh)R]^(+),when Q=S,Se,and Te)with nucleophilic beta-octamolybdate([β-Mo_(8)O_(26)]^(4-))result in supramolecular association.The main focus of such assembly is onσ-(Q^(IV))-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-Mo_(8)O_(26)]}complexes with cations stacked byπ-πinteractions;(ii)(Bu_(4)N)^(+),[Q(bPh)R]^(+)and[β-Mo_(8)O_(26)]^(4-)complexes of 2:2:1 stoichiometry withπ-πinteractions;(iii)(Bu4N)+,[Q(bPh)R]+and[β-Mo_(8)O_(26)]^(4-)complexes of a 2:2:1 stoichiometry withoutπ-πinteractions;and(iv){[Q(bPh)R]_(2)}_(2)[β-Mo_(8)O_(26)]salts withπ-πstacked cations but lacking any(Q^(IV))…O interactions.Moreover,interactions in the system can drive the reorganization of[β-Mo_(8)O_(26)]4-into[α-Mo_(8)O_(26)]^(4-).The halogen-bonded(Q^(IV))…O{(Q(bPh)R)_(x)[β-Mo_(8)O_(26)]^(4-)}(x=2 and 4)assemblies,π-πstacked 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.
