Synthesis, Structural Characterization and Photodecarbonylation Study of a Dicarbonyl Ruthenium(II)‐Bisquinoline Complex

Abstract

A photoactivatable ruthenium(II) carbonyl complex mer,cis ‐[Ru(II)Cl(BisQ)(CO) 2 ]PF 6 2 was prepared using a tridentate bisquinoline ligand (BisQ=(2,6‐diquinolin‐2‐yl)pyridin). Compound 2 was thoroughly characterized by standard analytical methods and single crystal X‐ray diffraction. The crystal structure of the complex cation reveals a distorted octahedral geometry. The decarbonylation upon exposure to 350 and 420 nm light was monitored by UV/VIS absorbance and Fourier transform infrared spectroscopies in acetonitrile and 1 % (v/v) DMSO in water, respectively. The kinetic of the photodecarbonylation has been elucidated by multivariate curve resolution alternating least‐squares analysis. The stepwise decarbonylation follows a serial mechanism. The first decarbonylation occurs very quickly whereas the second decarbonylation step proceeds more slowly. Moreover, the second rate constant is lower in 1 % (v/v) DMSO in water than in acetonitrile. In comparison to 350 nm irradiation, exposure to 420 nm light in acetonitrile results in a lower second rate constant.

Visible-to-NIR-Light Activated Release: From Small Molecules to Nanomaterials

“…The complexation of this photoCORM to bromozepam increased its antibacterial toxicity relative to the non-complexed drug. Complex 278 , which has a bisquinoline ligand, sequentially releases two equivalents of CO upon irradiation at 350 or 420 nm, with the first equivalent being liberated more efficiently . Finally, Oyama and co-workers recently introduced a series of Ru II dicarbonyl photoCORM complexes with asymmetric bipyridine ligands …”

Light‐Activated Carbon Monoxide Prodrugs Based on Bipyridyl Dicarbonyl Ruthenium(II) Complexes

“…The reaction rate of a photoreaction is best described by Equation . Conditional rate constants can be derived were (pseudo)first order kinetic is observed …”