The interaction of C-60, C-70, and C-60(CN)(2) radical anions with cobalt(II) tetraphenylporphyrin in solid multicomponent complexes

摘要

A method for the synthesis of the multicomponent ionic complexes: [Cr-I(C6H6)(2)(.divided by)][Co-II(tpp)(fullerene)(-)](.) C6H4Cl2, comprising bis(benzene)chromium (Cr(C6H6)(2)), cobalt(II) tetraphenylporphyrin (Co-II(tpp)), fullerenes (C-60, C-60(CN)(2), and C-70), and o-dichlorobenzene (C6H4Cl2) 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(C6H6)(2)}(.divided by)](1.7)[{Co-II(tpp)(C-60)}(2)](1.7-) . 33C(6)H(4)Cl(2) and [{Cr-I(C6H6)(2)}(.divided by)](2)[Co-II-(tPP){C-60(CN)(2)}](-)[C-60(CN)(2)(.-)].3C(6)H(4)C(2) are presented. The essentially shortened Co...C(fullerene) bond lengths of 2.28-2.32 Angstrom in these complexes indicate the formation of sigma-bonded [Co-II(tpp)][fullerene](-) anions, which are diamagnetic. All the ionic complexes are semiconductors with room temperature conductivity of 2 x 10(-3)-4 x 10(-6) Scm(-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(C6H6)(2), as well as the crystal structures of [Co-II-(tpp)](C-60).2.5 C6H4Cl2, [Co-II(tPP)](C-70).1.3CHCl(3).0.2C(6)H(6), and [Cr-0(C6H6)(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 Angstrom. [References: 62]