Homo‐ and Heterometallic [2×2] Grid Arrays Containing RuII, OsII, and FeII Subunits and their Mononuclear RuII and OsII Precursors: Synthesis, Absorption Spectra, Redox Behavior, and Luminescence Properties

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Abstract
The absorption spectra, redox behavior, and luminescence properties (both at 77 K in rigid matrices and at room temperature in fluid solution) of a series of [2×2] molecular grids have been investigated. The latter were prepared either by means of sequential self‐assembly, or by a stepwise protection/deprotection procedure, and are based on a ditopic hexadentate ligand 1 in which two terpyridine‐like binding sites are fused together in a linear arrangement. The molecular grids studied include the homometallic species [{Fe(1)}4]8+ (Fe2Fe2), and the heterometallic species [{Ru(1)}2{Fe(1)}2]8+ (Ru2Fe2) and [{Os(1)}2{Fe(1)}2]8+ (Os2Fe2). For comparison purposes, the properties of the mononuclear complexes [Ru(1)2]2+ (1‐Ru) and [Os(1)2]2+ (1‐Os) have been studied. All these compounds exhibit very intense absorption bands in the UV region (ε in the 105–106 M−1 cm−1 range, attributed to spin‐allowed ligand‐centered (LC) transitions), as well as intense metal‐to‐ligand charge‐transfer (MLCT) transitions (ε in the 104–105 M−1 cm−1 range) that extend to the entire visible region. The mononuclear species 1‐Ru and 1‐Os exhibit relatively intense luminescence, both in acetonitrile at room temperature (τ=59 and 18 ns, respectively) and in butyronitrile rigid matrices at 77 K. In contrast, the tetranuclear molecular grids do not exhibit any luminescence, either at room temperature or at 77 K. This is attributed to fast intercomponent energy transfer from the Ru‐ or Os‐based subunits to the low‐lying metal‐centered (MC) levels involving the FeII centers, which leads to fast radiationless decay. The redox behavior of the compounds is characterized by several metal‐centered oxidation and ligand‐centered reduction processes, most of them reversible in nature (as many as twelve for Fe2Fe2). Detailed assignment of each redox process has been made, and it is apparent that these systems can be viewed as multilevel molecular electronic species capable of reversibly exchanging a number of electrons at accessible and predetermined potentials. Furthermore, it is shown that the electronic interaction between specific subunits depends on their location in the structure and on the oxidation states of the other components.

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