Collect. Czech. Chem. Commun. 2003, 68, 1647-1662

A Solvent-Dependent and Electrochemically Controlled Self-Assembling/Disassembling System

Valeria Amendolaa, Massimo Boiocchib, Yuri Diaz Fernandezc, Carlo Manganoa and Piersandro Pallavicinia,*

a Dipartimento di Chimica Generale, Università di Pavia, via Taramelli 12, 27100 Pavia, Italy
b Centro Grandi Strumenti, Università di Pavia, via Bassi 6, 27100 Pavia, Italy
c Instituto Superior de Ciencias y de Tecnologias Nucleares, Ave. Salvador Allende y Luaces, Quinta de los Molinos, Plaza de la Ravolucion, Habana, Cuba


The bis-bidentate ligand R,S-1,2-diphenyl-N,N'-bis(2-quinolinemethylidene)ethane-1,2-diamine (ligand 4), containing two (iminomethyl)quinoline moieties separated by a cis-1,2-diphenylethylene spacer, forms stable complexes with both CuI and CuII. With CuII, the monomeric 1:1 complex [CuII(4)]2+ is obtained both in CH3CN and CH2Cl2. With CuI and overall 1:1 metal/ligand molar ratio, an equilibrium mixture is obtained in CH3CN, consisting of [CuI(4)2]+, [CuI2(4)2]2+ and [CuI2(4)(CH3CN)4]2+. The preponderant species is the two-metal one-ligand "open" complex [CuI2(4)(CH3CN)4]2+, in which each Cu+ cation is coordinated in a tetrahedral fashion by one (iminomethyl)quinoline unit and by two CH3CN molecules. Precipitation from the equilibrium mixture yields only crystals of [CuI2(4)(CH3CN)4](ClO4)2·2CH3CN, whose crystal and molecular structures have been determined. On the other hand, in the poorly coordinating CH2Cl2 solvent, only the dimeric helical [CuI2(4)2]2+ complex is obtained, when the overall metal/ligand 1:1 molar ratio is chosen. Addition of large quantities of acetonitrile to solutions of [CuI2(4)2]2+ in dichlorometane results in the formation of [CuI2(4)(CH3CN)4]2+, i.e. in the solvent-driven disassembling of the CuI helicate. While electrochemistry in CH3CN is poorly defined due to the presence of more than one CuI species, cyclic voltammetry experiments carried out in CH2Cl2 revealed a well defined behavior, with irreversible oxidation of [CuI2(4)2]2+ and irreversible reduction of [CuII(4)]2+ taking place at separate potentials (∆E ≈ 700 mV). Irreversibility and separation of the redox events are due to the self-assembling and disassembling processes following the reduction and oxidation, respectively.

Keywords: Helical structures; Electrochemistry; Molecular machines; Copper complexes; Imine ligands; Nitriles; Salenes; Quinolines; Chiral ligands; Cyclic voltammetry.

References: 30 live references.