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Issue 44, 2012
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Encapsulation controlled single molecule magnetism in tetrathiafulvalene-capped cyanide-bridged cubes

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Abstract

New TTF-based (TTF = tetrathiafulvalene) ligands, L1 and L2 (L1 = α-(4′-methyl-4,5-ethylenedithiotetrathiafulvalene-5′-thio)-α′-[tris-2,2,2-(1-pyrazolyl)ethoxy]-p-xylene and L2 = α-(4′-methyl-4,5-dimethylthiotetrathiafulvalene-5′-thio)-α′-[tris-2,2,2-(1-pyrazolyl)ethoxy]-p-xylene), possessing tris-pyrazolyl coordination sites, were synthesized. The reactions of Ni(BF4)2·6H2O with the TTF-ligands (L1 and L2), n-Bu4N[Fe(CN)3(tp or pztp)] (tp = hydrotris(pyrazol-1-yl)borate and pztp = tetrakis(pyrazol-1-yl)borate) in the presence of additional counter ions afforded two cyanide-bridged octanuclear complexes: [FeIII4NiII4(CN)12(pztp)4(L1)4](BF4)4 (1) and [FeIII4NiII4(CN)12(pztp)4(L2)4](PF6)4 (2). Using a similar procedure to that employed in the synthesis of complex 2, with the addition of sodium tetraphenylborate, yielded a two-electron-reduced compound, Na[FeIII2FeII2NiII4(CN)12(tp)4(L2)4](BF4)3 (3), in which a sodium ion was encapsulated by the cube. The host–guest complex 3 showed enhanced redox behaviour and while magnetic susceptibility measurements revealed ferromagnetic interactions to be operative in all three complexes, the cation encapsulation behaviour of 3 led it to exhibit single molecule magnet-type properties.

Graphical abstract: Encapsulation controlled single molecule magnetism in tetrathiafulvalene-capped cyanide-bridged cubes

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Publication details

The article was received on 26 Apr 2012, accepted on 11 Jul 2012 and first published on 09 Aug 2012


Article type: Paper
DOI: 10.1039/C2DT30908D
Citation: Dalton Trans., 2012,41, 13601-13608
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    Encapsulation controlled single molecule magnetism in tetrathiafulvalene-capped cyanide-bridged cubes

    K. Mitsumoto, H. Nishikawa, G. N. Newton and H. Oshio, Dalton Trans., 2012, 41, 13601
    DOI: 10.1039/C2DT30908D

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