Multicomponent Ionic Complexes of Cobalt( II ) Tetraphenylporphyrin with C 60 Fullerides − Transition from the σ‐Bonded [(Co II TPP)·(C 60 − )] Anion to Nonbonded Co II TPP and C 60 ·− Components

New multicomponent ionic complexes containing [(Cation + )·(C 60 − )] fullerides and neutral Co II TPP molecules were obtained [the cations are Cs + ( 1 ), tetramethylammonium (CH 3 ) 4 N + ( 2 ) and N ‐methylpyridinium N ‐MePy + ( 3 )]. The crystal structure of 1 determined from single‐crystal X‐ray diffraction analysis contains chains of alternating Co II TPP and C 60 ·− units with voids accommodating solvated [(Cs + )·(C 6 H 5 CN) 1.64 ]·CH 3 CN counter cations. Relatively long Co ··· C distances between Co II TPP and C 60 ·− in 1 (2.55−3.05 Å) indicate the absence of noticeable bonding of Co II TPP 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 Co II TPP, respectively. In contrast to 1 , complexes 2 and 3 contain EPR‐silent, σ‐bonded [(Co II TPP)·(C 60 − )] anions. The influence of the size of counter cations on the stability of σ‐bonded [(Co II TPP)·(C 60 − )] anions in ionic [(Cation + )·(Co II TPP)·(C 60 − )] complexes is analyzed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)