Indazole-Derived Mono-/Diruthenium and Heterotrinuclear Complexes: Switchable Binding Mode, Electronic Form, and Anion Sensing Events

Abstract

The article deals with the newer classes of mononuclear: [(acac)₂Ru^III(H-Iz)(Iz^-)] 1, [(acac)₂Ru^III(H-Iz)₂]ClO₄ [1]ClO₄/[1']ClO₄, and [(bpy)₂Ru^II(H-Iz)(Iz^-)]ClO₄ [2]ClO₄, mixed-valent unsymmetric dinuclear: [(acac)₂Ru^III(μ-Iz^-)₂Ru^II(bpy)₂]ClO₄ [3]ClO₄, and heterotrinuclear: [(acac)₂Ru^III(μ-Iz^-)₂M^II(μ-Iz^-)₂Ru^III(acac)₂] (M = Co:4a, Ni:4b, Cu:4c, and Zn:4d) complexes (H-Iz = indazole, Iz^- = indazolate, acac = acetylacetonate, and bpy = 2,2'-bipyridine). Structural characterization of all the aforestated complexes established their molecular identities including varying binding modes (N_a and N_b donors and 1H-indazole versus 2H-indazole) of the heterocyclic H-Iz/Iz^- in the complexes. Unlike [1']ClO₄ containing two NH protons at the backface of H-Iz units, the corresponding [1]ClO₄ was found to be unstable due to the deprotonation of its positively charged quaternary nitrogen center, and this resulted in the eventual formation of the parent complex 1. A combination of experimental and density functional theory calculations indicated the redox noninnocent feature of Iz^- in the complexes along the redox chain. The absence of intervalence charge transfer transition in the near-infrared region of the (Iz^-)₂-bridged unsymmetric mixed-valent Ru^IIIRu^II state in [3]ClO₄ suggested negligible intramolecular electronic coupling corresponding to a class I setup (Robin and Day classification). Heterotrinuclear complexes (4a-4d) exhibited varying spin configurations due to spin-spin interactions between the terminal Ru(III) ions and the central M(II) ion. Though both [3]ClO₄ and 4a-4d displayed ligand (Iz^-/Iz^•)-based oxidation, reductions were preferentially taken place at the bpy and metal (Ru^III/Ru^II) centers, respectively. Unlike 1 or [2]ClO₄ containing one free NH proton at the backface of H-Iz, [1']ClO₄ with two H-Iz units could selectively and effectively recognize F^-, OAc^-, and CN^- among the tested anions: F^-, OAc^-, CN^-, Cl^-, Br^-, I^-, SCN^-, HSO₄^-, and Η₂PΟ₄^- in CH₃CN via intermolecular NH···anion hydrogen bonding interaction. The difference in the sensing feature between [1']ClO₄ and 1/[2]ClO₄ could be rationalized by their pK_a values of 8.4 and 11.3/10.8, respectively.