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Title
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Fluorinated heterometallic -diketonates as volatile single-source precursors for the synthesis of low-valent mixed-metal fluorides
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Author
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Abstract
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| Hexafluoroacetylacetonates that contain lead and divalent first-row transition metals, PbM(hfac)4 (M = Ni (1), Co (2), Mn (3), Fe (4), and Zn (5)), have been synthesized. Their heterometallic structures are held together by strong Lewis acid−base interactions between metal atoms and diketonate ligands acting in chelating−bridging fashion. Compounds 1−5 are highly volatile and decompose below 350 °C. Fluorinated heterometallic β-diketonates have been used for the first time as volatile single-source precursors for the preparation of mixed-metal fluorides. Complex fluorides of composition Pb2MF6 have been obtained by decomposition of 1−5 in a two-zone furnace under low-pressure nitrogen flow. Lead−transition metal fluorides conform to orthorhombically distorted Aurivillius-type structure with layers of corner-sharing [MF6] octahedra separated by α-PbO-type (Pb2F2) blocks. Pb2NiF6 and Pb2CoF6 were found to exhibit magnetic ordering below 80 and 43 K, respectively. The ordering is antiferromagnetic, with a weak, uncompensated moment due to the canting of spins. The Pb2MF6 fluorides represent a new class of prospective magnetoelectric materials combining transition metals and lone-pair main-group cations. |
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Language
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English
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Source (journal)
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Journal of the American Chemical Society. - Washington, D.C., 1879, currens
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Publication
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Washington, D.C.
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American Chemical Society
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2011
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ISSN
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0002-7863
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DOI
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10.1021/JA109128R
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Volume/pages
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133
:4
(2011)
, p. 692-694
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ISI
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000287295300015
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Full text (Publisher's DOI)
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