Intercluster exchange pathways in polymer-chain molecular magnets Cu(hfac)2LR unveiled by electron paramagnetic resonance

Matvey V. Fedin, Sergey L. Veber, Ksenia Yu Maryunina, Galina V. Romanenko, Elizaveta A. Suturina, Nina P. Gritsan, Renad Z. Sagdeev, Victor I. Ovcharenko, Elena G. Bagryanskaya

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47 Citations (Scopus)

Abstract

Polymer-chain complexes Cu(hfac)2LR represent an interesting type of molecular magnets exhibiting thermally induced and light-induced magnetic switching, in many respects similar to a spin crossover. In the majority of these compounds the polymer chain consists of alternating one- and three-spin units composed of copper(II) ions and nitronyl nitroxides. The principal one-dimensional structure of the complexes has previously been assumed to play a key role in the observed magnetic anomalies. Using Q-band electron paramagnetic resonance (EPR) spectroscopy, we have reliably demonstrated that these complexes are indeed one-dimensional in the sense of the topology of their exchange channels; however, the magnetic chains spread across the structural polymer chains and consist solely of spin triads of nitroxide-copper(II)-nitroxide. Using four selected examples of complexes Cu(hfac)2LR, we have found the exchange coupling values between spin triads of neighboring polymer chains to range from <1 to ca. 10 cm-1. This conclusion could only be reached due to the selective probing of one- and three-spin units by EPR and correlates perfectly with both previous magnetic susceptibility data and quantum chemical calculations performed in this work. These findings give new insights into the cooperativity effects and mechanisms of magnetic anomalies in the Cu(hfac)2L R family of molecular magnets.

Original languageEnglish
Pages (from-to)13886-13891
Number of pages6
JournalJournal of the American Chemical Society
Volume132
Issue number39
DOIs
Publication statusPublished - 6 Oct 2010

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

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    Fedin, M. V., Veber, S. L., Maryunina, K. Y., Romanenko, G. V., Suturina, E. A., Gritsan, N. P., Sagdeev, R. Z., Ovcharenko, V. I., & Bagryanskaya, E. G. (2010). Intercluster exchange pathways in polymer-chain molecular magnets Cu(hfac)2LR unveiled by electron paramagnetic resonance. Journal of the American Chemical Society, 132(39), 13886-13891. https://doi.org/10.1021/ja105862w