Hydrogen bonding cavities regulating redox behavior and binding of metal-bound ligands

Binding of 3,5-di-tert-butyl-1,2-benzochatechol (H2DTBC) at Zn(II) complexes of a tetradentate, tripodal ligand L is significantly enhanced (36-4.6 x 10(4) fold), and its reduction potential shifted (90-270 mV) to more positive values by introducing one to three amino hydrogen bond donors. The structure of one of the (L)Zn(DTBC)] complexes is reported and shows intramolecular N-H...O hydrogen bonding between the ligand-based amino group and the Zn(II)-bound chatecholate, which provides an explanation for the observed behavior.