Second-Sphere Effects in Dinuclear FeZn Hydrolase Biomimetics: Tuning Binding and Reactivity Properties.

Herein, we report the synthesis and characterization of two dinuclear FeZn complexes [FeZnLP1] (1) and [FeZnLP2] (2), in which LP1 and LP2 are conjugated systems containing one and two pyrene groups, respectively, connected via the diamine -HN(CH)NH- spacer to the well-known NO-donor HL ligand (HL = 2-bis{[(2-pyridylmethyl)aminomethyl]-6-[(2-hydroxybenzyl)(2-pyridylmethyl)]aminomethyl}-4-methylphenol). The complex [FeZnL1] (3), in which HL was modified to HL1, with a carbonyl group attached to the terminal phenol group, was included in this study for comparison purposes. Both complexes 1 and 2 were satisfactorily characterized in the solid state and in solution.