The synthesis of a new Cu(II) derivative, [(biq-OH)CuCl2], (4,4-bis(hydroxymethyl)- 2,2-biquinoline (biq-OH)), and its reaction with potassium tropolonate (KTrop) is herein reported and the surprising results are discussed. Due to the steric requirements of the biq moiety, the tetrahedral geometry adopted by [(biq-OH)CuCl2] derivative makes it an unstable species, causing an overall rearrangement after reaction with KTrop, with competition between ligands and reduction of the copper ion. Indeed, a heteroleptic Cu(II) complex, [(biq- OH)Cu(Trop)Cl], and a ternary cocrystal, f[Cu(Trop)2][Cu(biq- OH)2]Clg(biq-OH), in which homoleptic Cu(II) and Cu(I) species coexist, could be isolated from the reaction mixture and characterized. Single crystal X-ray analysis of both the biq-OH ligand and the ternary cocrystal f[Cu(Trop)2][Cu(biq-OH)2]Clg(biq-OH) are reported and a deep analysis of the intermolecular interactions of their supramolecular assemblies in the solid crystalline state, conducted by Hirshfeld surface and contact enrichment tools, are thus reported.

The strange case of metal coordination in disubstituted-biquinolines: competition between ligands and formation of a hybrid organic/inorganic Cu(II)/Cu(I) ternary cocrystal

Scarpelli F.;La Deda M.;Godbert N.;Marino N.;Crispini A.
;
Aiello I.
2022-01-01

Abstract

The synthesis of a new Cu(II) derivative, [(biq-OH)CuCl2], (4,4-bis(hydroxymethyl)- 2,2-biquinoline (biq-OH)), and its reaction with potassium tropolonate (KTrop) is herein reported and the surprising results are discussed. Due to the steric requirements of the biq moiety, the tetrahedral geometry adopted by [(biq-OH)CuCl2] derivative makes it an unstable species, causing an overall rearrangement after reaction with KTrop, with competition between ligands and reduction of the copper ion. Indeed, a heteroleptic Cu(II) complex, [(biq- OH)Cu(Trop)Cl], and a ternary cocrystal, f[Cu(Trop)2][Cu(biq- OH)2]Clg(biq-OH), in which homoleptic Cu(II) and Cu(I) species coexist, could be isolated from the reaction mixture and characterized. Single crystal X-ray analysis of both the biq-OH ligand and the ternary cocrystal f[Cu(Trop)2][Cu(biq-OH)2]Clg(biq-OH) are reported and a deep analysis of the intermolecular interactions of their supramolecular assemblies in the solid crystalline state, conducted by Hirshfeld surface and contact enrichment tools, are thus reported.
Copper complexes; 2-20- biquinoline;
inorganic cocrystals
ternary cocrystals
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.11770/339707
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