Issue 32, 2009
From the journal:

Dalton Transactions

Effect of the Co–C(C60−) bond formation on magnetic properties of the ionic complex {cryptand[2,2,2]·(Na+)}·{CoIITPP·(C60−)}·(C6H4Cl2)2†

Dmitri V. Konarev,*a   Salavat S. Khasanov,b   Akihiro Otsuka,c   Gunzi Saito‡d  and  Rimma N. Lyubovskayaa  

* Corresponding authors

a Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region, Russia

b Institute of Solid State Physics RAS, Chernogolovka, Moscow region, Russia

c Research Center for Low Temperature and Materials Sciences, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan

d Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan

Abstract

A new ionic complex {cryptand[2,2,2]·(Na+)}·{CoIITPP·(C60−)}·(C6H4Cl2)2 has been obtained as single crystals by a diffusion technique. It involves coordination {CoIITPP·(C60−)} units and bulky {cryptand[2,2,2]·(Na+)} cations. The Co–C(C60−) coordination bond is short (2.262(2) Å at 100 K) which provides ordering in the C60− anions. This is the first ordered structure of {CoIITPP·(C60−)}. The coordination bonds weaken upon heating to be 2.316(4) Å at 250 K. As a result, the C60− anions begin to rotate at 250 K about the Co–C bond between two orientations. The complex is diamagnetic from 4 up to 320 K. The Co–C bonds dissociate above 320 K only to form unbound paramagnetic CoIITPP and C60˙− species. The process is accompanied by the reversible increase in magnetic susceptibility of the complex and the appearance of a new broad EPR signal with g = 2.1187 and a linewidth of ∼120 mT (350 K). The signal was attributed to both paramagnetic CoIITPP and C60˙−, which showed strong exchange interaction.

Graphical abstract: Effect of the Co–C(C60−) bond formation on magnetic properties of the ionic complex {cryptand[2,2,2]·(Na+)}·{CoIITPP·(C60−)}·(C6H4Cl2)2

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Article information

DOI
https://doi.org/10.1039/B904293H
Article type
Paper
Submitted
03 Mar 2009
Accepted
29 May 2009
First published
30 Jun 2009

Dalton Trans., 2009, 6416-6420

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Effect of the Co–C(C60−) bond formation on magnetic properties of the ionic complex {cryptand[2,2,2]·(Na+)}·{CoIITPP·(C60−)}·(C6H4Cl2)2

D. V. Konarev, S. S. Khasanov, A. Otsuka, G. Saito and R. N. Lyubovskaya, Dalton Trans., 2009, 6416 DOI: 10.1039/B904293H

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