Spin crossover induced by changing the identity of the secondary metal ion from PdII­ to NiII in a face-centered FeII8MII6 cubic cage

Hyunsung Min, Alexander R. Craze, Matthew J. Wallis, Ryuya Tokunaga, Takahiro Taira, Yutaka Hirai, Mohan M. Bhadbhade, Daniel J. Fanna, Christopher E. Marjo, Shinya Hayami, Leonard F. Lindoy, Feng Li

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)

Abstract

Discrete spin crossover (SCO) heteronuclear cages are a rare class of materials which have potential use in next-generation molecular transport and catalysis. Previous investigations of cubic cage [Fe8Pd6L8]28+ constructed using semi-rigid metalloligands, found that FeII centers of the cage did not undergo spin transition. In this work, substitution of the secondary metal center at the face of the cage resulted in SCO behavior, evidenced by magnetic susceptibility, Mössbauer spectroscopy and single crystal X-ray diffraction. Structural comparisons of these two cages shed light on the possible interplay of inter- and intramolecular interactions associated with SCO in the NiII analogue, 1 ([Fe8Ni6L8(CH3CN)12]28+). The distorted octahedral coordination environment, as well as the occupation of the CH3CN in the NiII axial positions of 1, prevented close packing of cages observed in the PdII analogue. This led to offset, distant packing arrangements whereby important areas within the cage underwent dramatic structural changes with the exhibition of SCO.

Original languageEnglish
Article numbere202203742
Number of pages9
JournalChemistry: A European Journal
Volume29
Issue number19
DOIs
Publication statusPublished - 3 Apr 2023

Bibliographical note

Publisher Copyright:
© 2022 Wiley-VCH GmbH.

Notes

WIP in RD

Keywords

  • cubic cage
  • heterometallic
  • spin crossover
  • metalloligand
  • spin transition

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