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

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 Zn^II center. The bipyridine-ligated zinc-flavonolate compound reported herein, namely bis(μ-4-oxo-2-phenyl-4H-chromen-3-olato)-κ³O³:O³,O⁴;κ³O³,O⁴:O³-bis[(2,2'-bipyridine-κ²N,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 Zn^II 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 d₆-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 Zn^II center.