Phosphoryl Group as a Strong σ-Donor Anionic Phosphine-Type Ligand: A Combined Experimental and Theoretical Study on Long-Lived Room Temperature Luminescence of the [Ru(tpy)(bpy)(Ph₂PO)]⁺ Complex

Abstract

A phosphoryl Ru(II) polypyridyl complex was prepared in a one-pot process. Theoretical analysis suggests that the phosphoryl ligand may be viewed as a strong σ-donor anionic phosphine L-type ligand. State-of-the-art free-energy profile calculations on the excited states demonstrate that both favorable thermodynamic and kinetic factors are responsible for the remarkable room temperature luminescence properties of the phosphoryl complex.

Anionic phosph(in)ito (“phosphoryl”) ligands: Non-classical “actor” phosphane-type ligands in coordination chemistry

“…We lately prepared in a one-pot process, starting from the secondary phosphane ruthenium polypyridyl complex 25 and following the deprotonation/oxidation sequence, the corresponding O−anionic 2+ 26 isolated in 92% yield as a red solid (Scheme 12, [73]). …”

“…Organophosphorus ligands, largely neglected in this domain, have the specific capacity in bringing up a large variety of electronic properties on the [Ru(tpy)(bpy)] 2+ metal core never achieved so far by their corresponding nitrogen ligands [73,217]. We lately report experimental evidences of a long-lived room temperature luminescent complex [Ru(tpy)(bpy){Ph 2 P(O -)}] 2+ 26 promoted by an O−anionic P-metalated phosphinito ligand (Fig.…”

“…Free energy profile on the excited states of O−anionic  1 -P−phosphinite [Ru(tpy)(bpy){(Ph 2 P(O -)}] 2+ 26 and [Ru(tpy)(bpy)(Ph 2 PH)] 2+ 25 complexes[73]. The ground state was omitted for clarity and the 3 MLCT states were deliberately placed at the same energy origin for comparison between the 3 MLCT and 3 MC excited states.…”

SBA‐15‐supported N‐coordinate ruthenium(II) materials bearing sulfonamide‐type ligands: Effect of ligand backbones on catalytic transfer hydrogenation of ketones and aldehydes

“…The steric–electronic parameters of N ‐donor complexes/materials must be modified by easily applied methods. Recently, ruthenium‐based catalysts have been used in various types of organic molecular synthesis such as reduction, transfer hydrogenation (TH), alkylation, etc …”

Computational characterization of competing energy and electron transfer states in bimetallic donor-acceptor systems for photocatalytic conversion

“…31–35 Specifically, quantum chemical calculations of the electron transfer (ET) and excitation energy transfer (EET) potential energy surfaces beyond the initially excited Franck-Condon region provided a more comprehensive theoretical understanding of the possible structural evolution accompanying photoinduced electronic processes for prototype light-harvesting transition metal complexes. 36–41 Many model photoactive D-A dyad systems comprised of one light harvesting Ru-complex 37–38, 42–44 coupled to a model Co-center 45–50 have been investigated. Donor-acceptor interactions have been widely studied and range from very weak to very strong, as nicely illustrated in the series of unbound (Ru|Co), weakly bound (Ru–Co), and tightly bound (Ru=Co) supramolecular Ru(II)-Co(III) systems studied by us and others.…”