A Red-Light-Driven CO-Releasing Complex: Photoreactivities and Excited-State Dynamics of Highly Distorted Tricarbonyl Rhenium Phthalocyanines

Chemistry. 2022 Aug 26;28(48):e202200716. doi: 10.1002/chem.202200716. Epub 2022 Jul 20.

Abstract

A complex comprising one [Re(CO)3 ]+ unit and a phthalocyanine (Pc) ligand (Re1 Pc) is shown to function as a photo-induced CO-releasing molecule (photoCORM) in the presence of O2 and a coordinative solvent under irradiation with red light, which can deeply penetrate living tissues. Transient absorption spectroscopic measurements indicate very short excited-state lifetimes and ultrafast intersystem crossing for Re1 Pc and Re2 Pc, which contains two [Re(CO)3 ]+ units. The excited-state properties are ascribed to efficient spin-orbit coupling and large Franck-Condon factors originating from the complexes' distorted structures, that is, unsymmetric coordination of [Re(CO)3 ]+ unit(s), one of which was confirmed by single-crystal X-ray analysis of a symmetrically substituted Pc with two [Re(CO)3 ]+ units. Re1 Pc represents a promising red-light-driven photoCORM that can be applied in biological environments or therapeutic applications.

Keywords: carbonyl ligands; photochemistry; photophysics; phthalocyanines; rhenium.

MeSH terms

  • Indoles
  • Isoindoles
  • Ligands
  • Light
  • Rhenium* / chemistry

Substances

  • Indoles
  • Isoindoles
  • Ligands
  • Rhenium
  • phthalocyanine