Electrochemical assembling/disassembling of helicates with hysteresis.

A series of eight tetradentate, ditopic, bisimino bisheterocyclic ligands (1-8), and their complexes with Cu(I) and Cu(II), have been studied in CH(3)CN solution, by means of (1)H NMR, mass, and UV/vis spectroscopy, while the crystal and molecular structure of the Cu(II) complexes [Cu(3)](CF(3)SO(3))(2) and [Cu(4)](CF(3)SO(3))(2) and of the Cu(I) complexes [Cu(2)(4)(2)](ClO(4))(2) and [Cu(2)(5)(2)](ClO(4))(2) have been determined by X-ray diffraction methods. The Cu(II) complexes are monomeric, almost square-planar structures, both in solution and in the solid state, while the Cu(I) complexes are two-metal, two-ligand dimers which can be both helical and "box-like" in the solid, while they adopt a simple helical configuration in acetonitrile solution. The systems made of ligands 1-8 and copper are bistable, as under the same conditions either the Cu(I) helical dimers or the Cu(II) monomers can be obtained and are stable. The electrochemical behavior of the 16 copper complexes has been studied in acetonitrile solutions by cyclic voltammetry. One reduction and one oxidation wave were found in all cases, which display no return wave and are separated by a 500-1000 mV interval. Irreversibility is due to the fast self-assembling process that follows the reduction of [Cu(II)(L)](2+) and to the fast disassembling process that follows the oxidation of [Cu(I)(2)(L)(2)](2+) (L = 1-8). However, the overall [oxidation+disassembling] or [reduction+self-assembling] processes, i.e., [Cu(I)(2)(L)(2)](2+) = 2[Cu(II)(L)](2+) + 2e(-), are fully reversible. Moreover, CV profiles show that solutions containing copper and L undergo hysteresis on changing the applied electrochemical potential: in the same potential interval, the systems can exist in solution as either [Cu(I)(2)(L)(2)](2+) or [Cu(II)(L)](2+), depending on the electrochemical history of the solution. Moreover, by changing the structural or donor features of the ligands it is possible to modulate the potentials at which the system undergoes a transition from one to the other of its two possible states, in the hysteresis cycle. In addition, the spectral properties of the Cu(I) and Cu(II) complexes of the considered ligands make these systems good candidates for storing information in solution, which can be electrochemically written or erased and spectroscopically read.

Molecular machines based on metal ion translocation.

Transition metal ions can be moved reversibly between the two coordinatively unequivalent compartments A and B of a ditopic ligand, using as an input the variation of a bulk solution parameter, either pH or redox potential. In a redox-driven translocation, the metal moves reversibly from A to B on cycling between two consecutive oxidation states (e.g., Cu(II)/Cu(I); Fe(III)/Fe(II)) by means of auxiliary oxidation and reduction reactions. In a pH-driven process, one compartment displays also acid-base properties (AH(n)() left arrow over right arrow A(n)(-) + nH(+)), and the M(n)(+) ion is translocated between B and A(n)(-) through consecutive addition of base and acid.

M and P double helical complexes of copper(I) with bis-imino bis-quinoline enantiomerically pure chiral ligands.

The enantiomerically pure bis-imino bis-quinoline ligands R,R-ImQ and S,S-ImQ have been prepared by Schiff condensation of 2-quinoline carboxyaldehyde with the pure R,R and S,S enantiomers of trans-1,2-diaminocyclohexane. Both ligands form 2:2 helical complexes with CuI perchlorate, and the crystal and molecular structure of [Cu2(R,R-ImQ)2]ClO4.H2O have been determined by X-ray diffraction methods: the [Cu2(R,R-ImQ)2]2+ molecular cation is a chiral double helix of M handedness, in which the two ligands are entertwined in such an arrangement that half of each ligand is not equivalent to the other half of the same ligand. Coupled circular dichroism and 1H NMR studies reveal that in CH3CN solution a rearrangement takes place toward a more symmetric helical structure (in which the two halves of the same ligand become equivalent), which maintains the same handedness found in the solid state and is a pure M isomer. Solid state and CH3CN solution CD experiments confirm that [Cu2(S,S-ImQ)2]ClO4.H2O, both in solution and in the solid state, is a pure double helix of P handedness, i.e., the enantiomer of the species containing the R,R ligand.