Dual Photoreactive Ternary Ruthenium(II) Terpyridyl Complexes: A Comparative Study on Visible-Light-Induced Single-Step Dissociation of Bidentate Ligands and Generation of Singlet Oxygen.

The versatile and tunable ligand-exchange dynamics in ruthenium(II)-polypyridyl complexes imposed by the modulation of the steric and electronic effects of the coordinated ligands provide an unlimited scope for developing phototherapeutic agents. The photorelease of a bidentate ligand from the Ru-center is better suited for potent Ru(II)-based photocytotoxic agents with two available labile sites for cross-linking with biological targets augmented with possible phototriggered 1 O 2 generation. Herein, we introduced a phenyl-terpyridine (ptpy) ligand in the octahedral Ru(II) core of [Ru(ptpy)(L-L)Cl] + to induce structural distortion for the possible photorelease of electronically distinct bidentate ligands (L-L). For a systematic study, we designed four Ru(II) polypyridyl complexes: [Ru(ptpy)(L-L)Cl](PF 6 ), ([ 1 ]-[ 4 ]), where L-L = 1,2-bis(phenylthio)ethane (SPH) [ 1 ], N , N , N ', N '-tetramethylethylenediamine (TMEN) [ 2 ], N 1, N 2-diphenylethane-1,2-diimine (BPEDI) [ 3 ], and bis[2-(diphenylphosphino)phenyl]ether (DPE-Phos) [ 4 ]. The detailed photochemical studies suggest a single-step dissociation of L-L from the bis-thioether (SPH) complex [ 1 ] and diamine (TMEN) complex [ 2 ], while no photosubstitution was observed for [ 3 ] and [ 4 ]. Complex [ 1 ] and [ 2 ] demonstrated a dual role, involving both photosubstitution and 1 O 2 generation, while [ 3 ] and [ 4 ] solely exhibited poor to moderate 1 O 2 production. The interplay of excited states leading to these behaviors was rationalized from the lifetimes of the 3 MLCT excited states by using transient absorption spectroscopy, suggesting intricate relaxation dynamics and 1 O 2 generation upon excitation. Therefore, the photolabile complexes [ 1 ] and [ 2 ] could potentially act as dual photoreactive agents via the phototriggered release of L-L (PACT) and/or 1 O 2 -mediated PDT mechanisms, while [ 4 ] primarily can be utilized as a PDT agent.