Photolability of NO in designed metal nitrosyls with carboxamido-N donors: a theoretical attempt to unravel the mechanism.

During the past few years, photoactive metal nitrosyls (NO complexes of metals) have drawn attention as potential drugs for delivery of nitric oxide (NO) to biological targets under the control of light. Major success in this area has been achieved with designed metal nitrosyls derived from ligands that contain carboxamide group(s). A number of iron, manganese and ruthenium {MNO}(6) nitrosyls of such kind exhibit excellent NO photolability under low-power visible and near-IR light. The results of theoretical studies on these NO-donors have provided insight into (a) the electronic transitions that lead to photorelease of NO and (b) the structural features of the ligands that dictate the sensitivity of the nitrosyls to light of specific wavelengths. In addition, the results have afforded clear understanding of the electronic configurations of the various nitrosyls. This article highlights these results in a coherent manner. Good matches between the predicted and observed spectral features and NO photolability strongly suggest that theoretical studies should be an integral part of the smart design of such NO-donors in the future research.

Fry NL ，Mascharak PK 《-》

Photoactive ruthenium nitrosyls as NO donors: how to sensitize them toward visible light.

Fry NL ，Mascharak PK 《-》

Ruthenium nitrosyls derived from polypyridine ligands with carboxamide or imine nitrogen donor(s): isoelectronic complexes with different NO photolability.

Rose MJ ，Patra AK ，Alcid EA ，Olmstead MM ，Mascharak PK ... -  《-》

Accelerated photorelease of NO from {Ru-NO}6 nitrosyls containing carboxamido-N and carboxylato-O donors: syntheses, structures, and photochemistry.

Halpenny GM ，Mascharak PK 《-》

Dye-tethered ruthenium nitrosyls containing planar dicarboxamide tetradentate N4 ligands: effects of in-plane ligand twist on NO photolability.

Fry NL ，Heilman BJ ，Mascharak PK 《-》