Theoretical Investigation of Phosphinidene Oxide Polypyridine Ruthenium(II) Complexes: Toward the Design of a New Class of Photochromic Compounds

Abstract

A DFT-based computational study performed in the gas phase and in acetonitrile on polypyridine ruthenium isomer complexes [Ru(tpy)(bpy)(POPh)](2+) and [Ru(tpy)(bpy)(OPPh)](2+) (bpy = 2,2'-bipyridine, tpy = 2,2':6',2″-terpyridine, Ph = phenyl) predicts that they constitute a prototype for a new family of inorganic photochromic systems. The two isomers are found to absorb in different spectral regions to excited states that are connected adiabatically through a thermodynamically and kinetically favorable triplet potential energy profile. Nonadiabatic routes were identified and shown to be preferable over the adiabatic mechanism. The reverse isomerization reaction is found to be achievable only thermally. The current predictive work will be of prime importance to experimentalists for the design of new inorganic phosphorus-based compounds with attractive photochromic properties.

Linkage Photoisomerization Mechanism in a Photochromic Ruthenium Nitrosyl Complex: New Insights from an MS-CASPT2 Study

“…These systems are based on linkage isomerizations between the metal center and ambidentate ligands. 13,14,15,16,17,18 Among these systems, ruthenium nitrosyl complexes have attracted growing interest over the past two decades, not only owing to their photochromic properties but also because of their capability to photorelease nitric oxide. 19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42 Despite extensive experimental investigations, the mechanism for these two competing processes remained unclear until recently.…”

“…44 The most significant contributions are based on density functional theory (DFT) calculations of the S®O linkage photoisomerization pathways in ruthenium and osmium sulfoxide complexes 45,46,47,48,49 and of the P®O linkage photoisomerization pathway in a phosphinidene oxide ruthenium complex. 18 Very recently, the N®O linkage photoisomerization pathway in the [RuCl(NO)(py)4] 2+ (where py denotes pyridine ligands) ruthenium nitrosyl complex, was investigated using a similar DFT-based strategy. 50 This study shed some light on the mechanistic picture of the N®O linkage photoisomerization.…”

On the Possible Coordination on a 3MC State Itself? Mechanistic Investigation Using DFT-Based Methods

“…Spectacular bond elongations and angular distortions have been characterized in numerous Ru(II) 3 MC states [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] and for other metals, e.g., Ir(III) [29][30][31]. Our contribution to the field covers photoisomerization mechanisms [32][33][34] and photoluminescence quenching mechanisms [35,36], as well as exploratory ruthenium(II) [37,38] and iron(II) [39][40][41][42] photophysics, in a constant dialogue with experimental chemists.…”

DFT analysis of the linkage isomerism in penta(ammine)ruthenium(II/III) complexes of benzotriazole: Natural bond orbital method approach and a comprehensive energy decomposition analysis

“…Regardless of the broad application of DFT method in chemistry, few cases addressed linkage isomerism in coordination compounds, and even fewer used the NBO approach …”

“…[31,32,41,42] Regardless of the broad application of DFT method in chemistry, few cases addressed linkage isomerism in coordination compounds, [21,[43][44][45][46][47][48][49][50][51][52][53][54][55][56][57] and even fewer used the NBO approach. [58][59][60][61][62] There are plenty schemes of energy decomposition analysis (EDA) besides the first proposed by Morokuma. [35] In the present work, we used the EDA scheme proposed by Su and Li (Su-LI EDA) in which the interaction energy (ΔE int ) between two fragments is decomposed into five components [eq.…”