Photodelivery of CO by designed photoCORMs: Correlation between absorption in the visible region and metal-CO bond labilization in carbonyl complexes

Abstract

The therapeutic potential of photoactive CO-releasing molecules (photoCORMs) have called for close examination of the roles of the ligand(s) and the central metal atoms on the overall photochemical labilization of the metal-CO bonds. Along this line, we have synthesized four metal complexes, namely, [MnBr(azpy)(CO)3] (1), [Mn(azpy)(CO)3(PPh 3)]ClO4 (2), [ReBr(azpy)(CO)3] (3), and [Re(azpy)(CO)3(PPh3)]ClO4 (4), derived from 2-phenylazopyridine. These complexes were characterized by spectroscopic and crystallographic studies. Although both 1 and 3 exhibit strong metal-to-ligand charge-transfer bands in the 500-600 nm region, only 1 photoreleases CO upon illumination with visible light. Results of theoretical studies were used to gain insight into this surprising difference. Strong spin-orbit coupling (prominent in heavy metals) appears to promote intersystem crossing to a triplet state in 3, a step that discourages CO release upon illumination with visible light. Slow release of CO from 2 and 4 also indicates that strong σ-donating ligands, such as Br-, accelerate the rate of CO photorelease relative to π-acid ligands, such as PPh3. Break it up! Despite strong absorptions in the visible range, [MnBr(azpy)(CO) 3] and [ReBr(azpy)(CO)3], two structurally and electronically similar metal-carbonyl complexes, exhibit very different CO photolability upon exposure to visible light. Our theoretical study results that explain these differences may be useful to future studies of photoactive CO-donating drugs triggered by visible/near-IR light. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.