Multicomponent ionic complexes of cobalt(II) tetraphenylporphyrin with C-60 fullerides - Transition from the sigma-bonded [((CoTPP)-T-II)center dot(C-60(-))] anion to nonbonded (CoTPP)-T-II and C-60(-) components

New multicomponent ionic complexes containing [(Cation(+)).(C-60(-))] fullerides and neutral (CoTPP)-T-II molecules were obtained [the cations are Cs+ (1), tetramethylammonium (CH3)(4)N+ (2) and N-methylpyridinium N-MePy+ (3)]. The crystal structure of I determined from single-crystal Xray diffraction analysis contains chains of alternating (CoTPP)-T-II and C-60(-) units with voids accommodating solvated [(Cs+).(C6H5CN)(1.64)].CH3CN counter cations. Relatively long Co...C distances between (CoTPP)-T-II and C-60(-) in 1 (2.55-3.05 Angstrom) indicate the absence of noticeable bonding of (CoTPP)-T-II and C-60(-). This is consistent with the EPR spectrum of 1, which manifests two EPR signals with g = 2.0009 and 2.4982 attributable to C-60(-) and (CoTPP)-T-II, respectively. In contrast to 1, complexes 2 and 3 contain EPR-silent, sigma-bonded [((CoTPP)-T-II).(C-60(-))] anions. The influence of the size of counter cations on the stability of sigma-bonded [((CoTPP)-T-II).(C-60(-))] anions in ionic [(Cation(+)).((CoTPP)-T-II).(C-60(-))] complexes is analyzed. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).