Defining the conditional basis of silicon phthalocyanine near-IR ligand exchange.

ABSTRACT: Bond cleavage reactions initiated by long-wavelength light are needed to extend the scope of the caged-uncaged paradigm into complex physiological settings. Axially unsymmetrical silicon phthalocyanines (SiPcs) undergo efficient release of phenol ligands in a reaction contingent on three factors - near-IR light (690 nm), hypoxia, and a thiol reductant. These studies detail efforts to define the mechanistic basis for this unique conditionally-dependent bond cleavage reaction. Spectroscopic studies provide evidence for the formation of a key phthalocyanine radical anion intermediate formed from the triplet state in a reductant-dependent manner. Computational chemistry studies indicate that phenol ligand solvolysis proceeds through a heptacoordinate silicon transition state and that this solv

SUBMITTER: Anderson ED 

PROVIDER: S-EPMC6344126 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature