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The peculiar redox-active character of quinonoid metal complexes makes them extremely appealing to design materials of potential technological interest. We show here how the tuning of the properties of these systems can be pursued by using appropriate molecular synthetic techniques. In particular, we focus our attention on metal polyoxolene complexes exhibiting intramolecular electron transfer processes involving either the ligand and the metal ion or the two dioxolene moieties of a properly designed ligand thus inducing electronic bistability. The transition between the two metastable electronic states can be induced by different external stimuli such as temperature, pressure, light, or pH suggesting the use of these systems for molecular switches.

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A series of cobalt complexes [Co(Me(n)tpa)(diox)]PF(6)sol (diox=3,5-di-tert-butyl-1,2-dioxolene; sol=ethanol, toluene; tpa=tris(2-pyridylmethyl)amine) were prepared by using tripod-like Me(n)tpa (n=0, 1, 2, 3), derived from tpa by successive introduction of methyl groups into the 6-position of the pyridine moieties, as an ancillary ligand. The steric hindrance induced by this substitution modulates the redox properties of the metal acceptor, thus determining the charge distribution of the metal-dioxolene moiety at room temperature. All of these complexes were characterised by using diffractometric studies, electronic spectroscopic analysis, and magnetic susceptibility measurements. In the solid state, the [Co(Me(n)tpa)(diox)](+) ions (n=0, 1) can be described as diamagnetic cobalt(III)-catecholato derivatives, whereas a cobalt(II)-semiquinonato description seems appropriate for the paramagnetic [Co(Me(3)tpa)(diox)](+) complex. The complex [Co(Me(2)tpa)(diox)]PF(6)C(2)H(5)OH undergoes entropy-driven valence tautomeric interconversion at room temperature. Optically induced valence tautomerism was observed by irradiation of [Co(Me(n)tpa)(diox)]PF(6) complexes (n=0, 1, 2) at cryogenic temperatures. The different relaxation kinetics of the photoinduced metastable phases are related to the respective free-energy changes of the interconversion, as estimated by cyclic voltammetric experiments at room temperature, and to the different lattice interactions, as supported by structural data. These results show the importance of molecular techniques for controlling the relaxation properties of photoinduced metastable species. At the same time, this behaviour strongly suggests that this paradigm exhibits intrinsic limits because of the less controllable factors that affect the process.

A photoswitchable system that undergoes entropy-driven valence tautomerism has been obtained by successfully tuning the electronic properties of a dinuclear cobalt-polyoxolene complex by molecular techniques. For more information see the Communication by A. Dei, J.-F. Létard, and co-workers on the following pages.

A solvent tune: The crystallization solvent affects the temperature and light dependence of the valence tautomeric behaviour of a 1:1 Co–dioxolene compound, thus offering a new possibility of tuning its charge distribution (see figure). This approach paves the way for the development of molecular magnetic materials whose properties may be controlled by chemical means.

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The 3,5-di-tert-butyl-catecholato and 9,10-phenanthrenecatecholato adducts of the cobalt-tetraazamacrocycle complex Co(Me(4)cyclam)(2+) (Me(4)cyclam = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) were synthesized and oxidized. The oxidation reaction products were isolated in the solid state as hexafluorophosphate derivatives. Both these complexes can be formulated as 1:1 cobalt(II)-semiquinonato complexes, that is, Co(Me(4)cyclam)(DBSQ)PF(6) (1) and Co(Me(4)cyclam)(PhSQ)PF(6) (2), in the temperature range 4-300 K, in striking contrast with the charge distribution found in similar adducts formed by related tetraazamacrocycles. The synthesis strategy and the structural, spectroscopic, and magnetic properties are reported and discussed. The crystallographic data for 2 are as follows: monoclinic, space group P2(1)/a, nomicron. 14, a = 14.087(4) A, b = 15.873(4) A, c = 14.263 (7) A, alpha = 89.91(3) degrees, beta = 107.34(2) degrees, gamma = 90.08(2) degrees, Z = 4. Both these complexes are characterized by triplet electronic ground states arising from the antiferromagnetic coupling between the high-spin d(7) metal ion and the radical ligand.