The Interaction of C 60 , C 70 , and C 60 (CN) 2 Radical Anions with Cobalt( II ) Tetraphenylporphyrin in Solid Multicomponent Complexes

A method for the synthesis of the multicomponent ionic complexes: [Cr I (C 6 H 6 ) 2 .+ ][Co II (tpp)(fullerene) − ] ⋅ C 6 H 4 Cl 2 , comprising bis(benzene)chromium (Cr(C 6 H 6 ) 2 ), cobalt( II ) tetraphenylporphyrin (Co II (tpp)), fullerenes (C 60 , C 60 (CN) 2 , and C 70 ), and o ‐dichlorobenzene (C 6 H 4 Cl 2 ) has been developed. The monoanionic state of the fullerenes has been proved by optical absorption spectra in the UV/vis/NIR and IR ranges. The crystal structures of the ionic [{Cr I (C 6 H 6 ) 2 } .+ ] 1.7 [{Co II (tpp)(C 60 )} 2 ] 1.7− ⋅ 3.3 C 6 H 4 Cl 2 and [{Cr I (C 6 H 6 ) 2 } .+ ] 2 [Co II (tpp){C 60 (CN) 2 }] − [C 60 (CN) 2 .− ]) ⋅ 3 C 6 H 4 Cl 2 are presented. The essentially shortened Co ⋅⋅⋅ C(fullerene) bond lengths of 2.28–2.32 Å in these complexes indicate the formation of σ ‐bonded [Co II (tpp)][fullerene] − anions, which are diamagnetic. All the ionic complexes are semiconductors with room temperature conductivity of 2×10 −3 –4×10 −6 S cm −1 , and their magnetic susceptibilities show Curie–Weiss behavior. The neutral complexes of Co II (tpp) with C 60 , C 60 (CN) 2 , C 70 , and Cr 0 (C 6 H 6 ) 2 , as well as the crystal structures of [Co II (tpp)](C 60 ) ⋅ 2.5 C 6 H 4 Cl 2 , [Co II (tpp)](C 70 ) ⋅ 1.3 CHCl 3 ⋅ 0.2 C 6 H 6 , and [Cr 0 (C 6 H 6 ) 2 ][Co II (tpp)] are discussed. In contrast to the ionic complexes, the neutral ones have essentially longer Co ⋅⋅⋅ C(fullerene) bond lengths of 2.69–2.75 Å.