Organostannoxane-supported multiferrocenyl assemblies: synthesis, novel supramolecular structures, and electrochemistry

Abstract

Organostannoxane-based multiredox assemblies containing ferrocenyl peripheries have been readily synthesized by a simple one-pot synthesis, either by a solution method or by room-temperature solid-state synthesis, in nearly quantitative yields. The number of ferrocenyl units in the multiredox assembly is readily varied by stoichiometric control as well as by the choice of the organotin precursors. Thus, the reaction of the diorganotin oxides, R₂SnO (R=Ph, nBu and tBu) with ferrocene carboxylic acid affords tetra-, di-, and mononuclear derivatives [{Ph₂Sn[OC(O)Fc]₂}₂] (1), [{[nBu₂SnOC(O)Fc]₂O}₂] (2), [nBu₂Sn{OC(O)Fc}₂] (3), [{tBu₂Sn(OH)OC(O)Fc}₂] (4), and [tBu₂Sn{OC(O)Fc}₂] (5) (Fc=η ⁵C₅H₄-Fe-η⁵C₅H₅). The reaction of triorganotin oxides, R₃SnOSnR₃ (R=nBu and Ph) with ferrocene carboxylic acid leads to the formation of the mono-nuclear derivatives [Ph₃SnOC(O)Fc] (6) and [{nBu₃SnOC(O)Fc}_n] (7). Molecular structures of the compounds 1-4 and 6 have been determined by single-crystal X-ray analysis. The molecular structure of compound 1 is new among organotin carboxylates. In this compound, ferrocenyl carboxylates are involved in both chelating and bridging coordination modes to the tin atoms to form an eight-membered cyclic structure. In all of these compounds, the acidic protons of the cyclopentadienyl groups are hydrogen bonded to the carboxylate oxygens (C=H···O) to form rich supramolecular assemblies. In addition to this, π -π , T-shaped, L-shaped, and side-to-face stacking interactions involving ferrocenyl groups also occur. Compound 6 shows an interesting and novel intermolecular CO₂-π stacking interaction. Electrochemical analysis of the compounds 1-4, 6, and 7 shows a single, quasi-reversible oxidation peak corresponding to the simultaneous oxidation of four, two, and one ferrocenyl substituents, respectively. Compound 5 shows two quasi-reversible oxidation peaks. This is attributed to the positional difference among the ferrocenyl substituents on the tin atom. Additionally, while compounds 2 and 4 are electrochemically quite robust and do not decompose even after ten continuous CV cycles, compounds 1, and 3, 5-7 start to show decomposition after five cycles.