Distinctive Aspects in Aquation, Proton-Coupled Redox, and Photoisomerization Reactions between Geometric Isomers of Mononuclear Ruthenium Complexes with a Large-π-Conjugated Tetradentate Ligand

Geometric isomers of mononuclear ruthenium(II) complexes, distal-/proximal-[Ru(tpy)(dpda)Cl]⁺ (d-/p-RuCl, tpy = 2,2′:6′,2″-terpyridine, dpda = 2,7-bis(2-pyridyl)-1,8-diazaanthracene), were newly synthesized to comprehensively investigate the geometric and electronic structures and distinctive aspects in various reactions between isomers. The ultraviolet (UV)–visible absorption spectra of d-/p-RuCl isomers show intense bands for metal-to-ligand charge transfer (MLCT) at close wavelengths of 576 and 573 nm, respectively. However, time-dependent density functional theory (TD-DFT) calculations suggest that the MLCT transition of d-RuCl involves mainly single transitions to the π* orbital of the dpda ligand in contrast to mixing of the π* orbitals of the dpda and tpy ligands for p-RuCl. The aquation reaction (1.5 × 10^–3 s^–1) of p-RuCl to yield proximal-[Ru(tpy)(dpda)(OH₂)]²⁺ (p-RuH₂O) is faster than that (5.3 × 10^–6 s^–1) of d-RuCl in D₂O/CD₃OD (4:1 v/v) by three orders of magnitude, which resulted from the longer Ru–Cl bond by 0.017 Å and the distorted angle (100.2(3)°) of Cl–Ru–N (a nitrogen of dpda, being on a tpy plane) due to the steric repulsion between Cl and dpda for p-RuCl. Electrochemical measurements showed that d-RuH₂O undergoes a 2-step oxidation reaction of 1H⁺-coupled 1e^– processes of Ru^II–OH₂/Ru^III–OH and Ru^III–OH/Ru^IVO at pH 1–9, whereas p-RuH₂O undergoes a 1-step oxidation reaction of a 2H⁺-coupled 2e^– process of Ru^II–OH₂/Ru^IVO in the pH range of pH 1–10. The irreversible photoisomerization from d-RuH₂O to p-RuH₂O was observed in aqueous solution with an internal quantum yield (Φ) of 5.4 × 10^–3% at 520 nm, which is lower compared with Φ = 1.1–2.1% of mononuclear Ru(II) aquo complexes with similar bidentate ligands instead of dpda by three orders of magnitude. This is possibly ascribed to the faster nonradiative decay rate from the excited ³MLCT state to the ground state for d-RuH₂O due to the lower π* level of dpda ligands according to the energy-gap law: the rate decreases exponentially with the increasing energy gap.