A bipyridine-ligated zinc(II) complex with bridging flavonolate ligation: synthesis, characterization, and visible-light-induced CO release reactivity

Abstract

Metal–flavonolate compounds are of significant current interest as synthetic models for quercetinase enzymes and as bioactive compounds of importance to human health. Zinc–3-hydroxyflavonolate compounds, including those of quercetin, kampferol, and morin, generally exhibit bidentate coordination to a single ZnII center. The bipyridine-ligated zinc–flavonolate compound reported herein, namely bis(μ-4-oxo-2-phenyl-4H-chromen-3-olato)-κ3 O 3:O 3,O 4;κ3 O 3,O 4:O 3-bis[(2,2′-bipyridine-κ2 N,N′)zinc(II)] bis(perchlorate), {[Zn2(C15H9O3)2(C10H8N2)2](ClO4)2} n , (1), provides an unusual example of bridging 3-hydroxyflavonolate ligation in a dinuclear metal complex. The symmetry-related ZnII centers of (1) exhibit a distorted octahedral geometry, with weak coordination of a perchlorate anion trans to the bridging deprotonated O atom of the flavonolate ligand. Variable-concentration conductivity measurements provide evidence that, when (1) is dissolved in CH3CN, the complex dissociates into monomers. 1H NMR resonances for (1) dissolved in d 6-DMSO were assigned via HMQC to the H atoms of the flavonolate and bipyridine ligands. In CH3CN, (1) undergoes quantitative visible-light-induced CO release with a quantum yield [0.004 (1)] similar to that exhibited by other mononuclear zinc–3-hydroxyflavonolate complexes. Mass spectroscopic identification of the [(bpy)2Zn(O-benzoylsalicylate)]+ ion provides evidence of CO release from the flavonol and of ligand exchange at the ZnII center.