Fluorinated heterometallic β-diketonates as volatile single-source precursors for the synthesis of low-valent mixed-metal fluorides

Anantharamulu Navulla, Alexander A. Tsirlin, Artem M. Abakumov, Roman V. Shpanchenko, Haitao Zhang, Evgeny V. Dikarev

Research output: Contribution to journalArticlepeer-review

33 Citations (Scopus)

Abstract

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. Pb2NiF 6 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 Pb 2MF6 fluorides represent a new class of prospective magnetoelectric materials combining transition metals and lone-pair main-group cations.

Original languageEnglish
Pages (from-to)692-694
Number of pages3
JournalJournal of the American Chemical Society
Volume133
Issue number4
DOIs
Publication statusPublished - 2 Feb 2011
Externally publishedYes

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