The Interaction of C60, C70, and C60(CN)2 radical anions with cobalt(II) tetraphenylporphyrin in solid multicomponent complexes

Dmitri V Konarev; Salavat S Khasanov; Gunzi Saito; Rimma N Lyubovskaya; Yukihiro Yoshida; Akihiro Otsuka

doi:10.1002/chem.200204470

The Interaction of C60, C70, and C60(CN)2 radical anions with cobalt(II) tetraphenylporphyrin in solid multicomponent complexes

Chemistry. 2003 Aug 18;9(16):3837-48. doi: 10.1002/chem.200204470.

Authors

Dmitri V Konarev¹, Salavat S Khasanov, Gunzi Saito, Rimma N Lyubovskaya, Yukihiro Yoshida, Akihiro Otsuka

Affiliation

¹ Division of Chemistry, Graduate School of Science Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan. konarev@icp.ac.ru

PMID: 12916108
DOI: 10.1002/chem.200204470

Abstract

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 A 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) 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 A.