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Issue 34, 2014
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Design, crystal structures and magnetic properties of anionic salts containing fullerene C60 and indium(III) bromide phthalocyanine radical anions

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Abstract

Two salts containing fullerene C60 and indium(III) bromide phthalocyanine (Pc) radical anions have been obtained as single crystals: (TBA+)3(C60˙){InIII(Br)(Pc)˙}(Br)·C6H4Cl2 (1) and (TEA+)2(C60˙){InIII(Br)(Pc)˙}·C6H4Cl2·C6H14 (2) where TBA+ and TEA+ are tetrabutyl- and tetraethylammonium cations, respectively. The presence of both radical anions is supported by spectra of 1 and 2 in the NIR and IR-ranges. The salts contain zigzag C60˙ chains with 10.136 and 10.383 Å center-to-center (ctc) distances in 1 and a uniform ctc distance of 10.186 Å in 2. In 1, the C60˙ radical anions are dimerized in the 180–140 K range to form singly bonded (C60)2 dimers, whereas they remain monomeric in 2. Effective packing of planar In(Br)(Pc)˙ and spherical C60˙ is attained by introducing fullerene spheres between the phenylene substituents of Pc allowing the formation of multiple van der Waals contacts between them. The effective magnetic moment of 1 at 300 K is 2.35μB, indicating a contribution of both C60˙ and In(Br)(Pc)˙ species having S = 1/2 spin state. There is strong antiferromagnetic coupling of spins between fullerenes in the chains and fullerenes and phthalocyanines in the monomeric phase of 1 with the Weiss temperature of −120 K in the 300–180 K range. The formation of diamagnetic (C60)2 dimers switches off magnetic coupling and magnetically isolates In(Br)(Pc)˙ (Weiss temperature is only −1 K in the 140–10 K range). Magnetic behavior of 2 is described by the Curie–Weiss law with weak ferromagnetic coupling of spins with Θ = +7.6 K in the 50–300 K range. Both salts manifest single Lorentzian EPR lines at room temperature with g = 1.9911 and a linewidth (ΔH) of 25.4 mT (1) and g = 1.9956 and ΔH = 7.5 mT (2) which can be attributed to both C60˙ and In(Br)(Pc)˙ species having strong exchange interaction. An asymmetric signal with the main component at g = 1.989–1.965 in the dimeric phase of 1 was attributed to the In(Br)(Pc)˙ radical anions.

Graphical abstract: Design, crystal structures and magnetic properties of anionic salts containing fullerene C60 and indium(iii) bromide phthalocyanine radical anions

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The article was received on 19 Apr 2014, accepted on 01 Jul 2014 and first published on 02 Jul 2014


Article type: Paper
DOI: 10.1039/C4DT01153H
Author version available: Download Author version (PDF)
Citation: Dalton Trans., 2014,43, 13061-13069
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    Design, crystal structures and magnetic properties of anionic salts containing fullerene C60 and indium(III) bromide phthalocyanine radical anions

    D. V. Konarev, A. V. Kuzmin, S. S. Khasanov, A. Otsuka, H. Yamochi, G. Saito and R. N. Lyubovskaya, Dalton Trans., 2014, 43, 13061
    DOI: 10.1039/C4DT01153H

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