Katarzyna Grubel - Influence of Supporting Ligand Microenvironment on the Aqueous Stability and Visible Light Induced CO-Release Reactivity of Zinc Flavonolato Species

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      Publication Details (including relevant citation   information):

      Anderson, S. N.; Noble, M.; Grubel, K.; Marshall, B.; Arif, A.   M.; Berreau, L. M. Journal of Coordination Chemistry,   2014, 1-33.



      The visible   light-induced CO-release reactivity of the zinc flavonolato   complex [(6-Ph2TPA)Zn(3-Hfl)]ClO4 (1) has been investigated in 1   : 1 H2O : DMSO. Additionally, the effect of ligand secondary   microenvironment on the aqueous stability and visible   light-induced CO-release reactivity of zinc flavonolato species   has been evaluated through the preparation, characterization, and   examination of the photochemistry of compounds supported by   chelate ligands with differing secondary appendages,   [(TPA)Zn(3-Hfl)]ClO4 (3; TPA = tris-2-(pyridylmethyl)amine) and   [(bnpapa)Zn(3-Hfl)]ClO4 (4; bnpapa =   N,N-bis((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine)).   Compound 3 undergoes reaction in 1 : 1 H2O : DMSO resulting in   the release of the free neutral flavonol. Irradiation of   acetonitrile solutions of 3 and 4 at 419 nm under aerobic   conditions results in quantitative, photoinduced CO-release.   However, the reaction quantum yields under these conditions are   lower than that exhibited by 1, with 4 exhibiting an especially   low quantum yield. Overall, the results of this study indicate   that positioning a zinc flavonolato moiety within a hydrophobic   microenvironment is an important design strategy toward further   developing such compounds as CO-release agents for use in   biological systems.

      Address (URL): http://www.tandfonline.com/doi/abs/10.1080/00958972.2014.977272#.VcOmt5fGqy4