Abstract
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, trans-[RuCl(NO)(py)4]2+, trans-[RuBr(NO)(py)4]2+, and trans-(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.
Highlights
Photochromic systems are made of photoswitchable molecular building blocks, which often undergo a photoisomerization process [1,2,3]
In the the results of calculations showcalculations that the main of photoconversion following, wethese present the resultsand of these andreason show for thatthe thedecrease main reason for the decrease efficiency in this series of complexes involves an increase of the photoproduct absorption at the of photoconversion efficiency in this series of complexes involves an increase of the photoproduct irradiation wavelength rather than a change in the photoisomerization pathways
Because of the large barrier occurring along the adiabatic triplet photoisomerization pathway, funnels for efficient non-radiative decay paths between the lowest triplet excited state and the singlet ground state were located by optimizing minimum energy crossing points (MECP) between these two states
Summary
Juan Sanz García 1,2, * ID , Francesco Talotta 1 , Fabienne Alary 1 , Isabelle M. Dixon 1 , Jean-Louis Heully 1 and Martial Boggio-Pasqua 1, * ID. Present address: Institut de Recherche de Chimie Paris, PSL Research University, CNRS, Chimie ParisTech, 11 Rue Pierre et Marie Curie, F-75005 Paris, France
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