A Theoretical Study of the N to O Linkage Photoisomerization Efficiency in a Series of Ruthenium Mononitrosyl Complexes

• Published in: Molecules (Basel, Switzerland) Vol. 22; no. 10; p. 1667
• Main Authors: García, Juan Sanz, Talotta, Francesco, Alary, Fabienne, Dixon, Isabelle M, Heully, Jean-Louis, Boggio-Pasqua, Martial
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 06.10.2017; MDPI
• Subjects: Absorption; Chemical Sciences; computational photochemistry; Coordination Complexes - chemistry; Coordination Complexes - radiation effects; Density functional theory; Efficiency; Energy; Irradiation; Isomerism; Kinetics; Ligands; Light; Models, Molecular; Molecular Structure; Nitric Oxide - chemistry; Optical properties; or physical chemistry; photochromism; photoisomerization; Quantum Theory; Ruthenium; Ruthenium - chemistry; Single crystals; Theoretical and; Thermodynamics; photoisomerization; computational photochemistry; photochromism; density functional theory
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules22101667

Ruthenium nitrosyl complexes are fascinating versatile photoactive molecules that can either undergo NO linkage photoisomerization or NO photorelease. The photochromic response of three ruthenium mononitrosyl complexes, -[RuCl(NO)(py)₄] , -[RuBr(NO)(py)₄] , and -(Cl,Cl)[RuCl₂(NO)(tpy)]⁺, has been investigated using density functional theory and time-dependent density functional theory. The N to O photoisomerization pathways and absorption properties of the various stable and metastable species have been computed, providing a simple rationalization of the photoconversion trend in this series of complexes. The dramatic decrease of the N to O photoisomerization efficiency going from the first to the last complex is mainly attributed to an increase of the photoproduct absorption at the irradiation wavelength, rather than a change in the photoisomerization pathways.