Ruthenium Azobis(benzothiazole): Electronic Structure and Impact of Substituents on the Electrocatalytic Single-Site Water Oxidation Process

The present article deals with the structurally and spectroelectrochemically characterized newer class of ruthenium-azoheteroarenes [Ru^II(Ph-trpy)(Cl)(L)]ClO₄, [1]ClO₄-[3]ClO₄ (Ph-trpy: 4'-phenyl-2,2':6',2″-terpyridine; L1: 2,2'-azobis(benzothiazole) ([1]ClO₄); L2: 2,2'-azobis(6-methylbenzothiazole) ([2]ClO₄); L3: 2,2'-azobis(6-chlorobenzothiazole) ([3]ClO₄)). A collective consideration of experimental (i.e., structural and spectroelectrochemical) and theoretical (DFT calculations) results of [1]ClO₄-[3]ClO₄ established selective stabilization of (i) the unperturbed azo (N═N)⁰ function of L, (ii) the exclusive presence of the isomeric form involving the N(azo) donor of L trans to Cl, and (iii) the presence of extended, hydrogen-bonded trimeric units in the asymmetric unit of [2]ClO₄ (CH---O) via the involvement of ClO₄^- anions. The detailed electrochemical studies revealed metal-based oxidation of [Ru^II(Ph-trpy)(Cl)(L)]⁺ (1⁺-3⁺) to [Ru^III(Ph-trpy)(Cl)(L)]²⁺ (1²⁺-3²⁺); however, the electronic form of the first reduced state (1-3) could be better represented by its mixed Ru^II(Ph-trpy)(Cl)(L^•-)/Ru^III(Ph-trpy)(Cl)(L^2-) state. Both native (1⁺-3⁺) and reduced (1-3) states exhibited weak lower energy transitions within the range of 1000-1200 nm. Further, [1]ClO₄-[3]ClO₄ delivered an electrochemical OER (oxygen evolution reaction) process in alkaline medium on immobilizing them to a carbon cloth support, which divulged an amplified water oxidation feature for [2]ClO₄ due to the presence of electron-donating methyl groups in the L2 backbone. The faster OER kinetics and high catalytic stability of [2]ClO₄ could also be rationalized by its lowest Tafel slope (85 mV dec^-1) and choronoamperometric experiment (stable up to 12 h), respectively, along with high Faradic efficiency (∼97%). A comparison of [2]ClO₄ with the reported analogous ruthenium complexes furnished its excellent intrinsic water oxidation activity.