Tunable valence tautomerism in lanthanide–organic alloys

Maja A. Dunstan*, Anna S. Manvell, Nathan J. Yutronkie, Frédéric Aribot, Jesper Bendix, Andrei Rogalev, Kasper S. Pedersen*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

The inimitable electronic structures of the lanthanide (Ln) ions are key to advanced materials and technologies involving these elements. The trivalent ions are ubiquitous and are used much more widely than the divalent and tetravalent analogues, which possess vastly different optical and magnetic properties. Hence, alteration of the valence electron count by external stimuli can lead to dramatic changes in materials properties. Compounds exhibiting a temperature-induced complete Ln(III) ⇄ Ln(II) switch, referred to as a valence tautomeric (VT) transition, are rare. Here we present an abrupt and hysteretic VT transition in a lanthanide-based coordination polymer, SmI2(pyrazine)3, driven by the interconversion of Sm(II)–pyrazine(0) and Sm(III)–pyrazine(·−) redox pairs. Alloying SmI2(pyrazine)3 with Yb(II) yields isomorphous Sm1–xYbxI2(pyrazine)3 solid solutions with VT transition critical temperatures ranging widely from 200 K to ∼50 K at ambient pressure. These findings demonstrate a simple strategy to realize thermally switchable magnetic materials with chemically tunable transition temperatures. (Figure presented.)

Original languageEnglish
JournalNature Chemistry
Number of pages8
ISSN1755-4330
DOIs
Publication statusAccepted/In press - 2024

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