Precise control and consecutive modulation of spin transition temperature using chemical migration in porous coordination polymers

Ryo Ohtani, Ko Yoneda, Shuhei Furukawa, Nao Horike, Susumu Kitagawa, Ana B. Gaspar, M. Carmen Muñoz, José A. Real, Masaaki Ohba

Research output: Contribution to journalArticle

140 Citations (Scopus)

Abstract

Precise control of spin transition temperature (Tc) is one of the most important challenges in molecular magnetism. A Hofmann-type porous coordination polymer {Fe(pz)[PtII(CN)4]} (1; pz = pyrazine) exhibited cooperative spin transition near room temperature (T cup = 304 K and Tcdown = 284 K) and its iodine adduct {Fe(pz)[PtII/IV(CN)4(I)]} (1-I), prepared by oxidative addition of iodine to the open metal sites of Pt II, raised the Tc by 100 K. DSC and microscopic Raman spectra of a solid mixture of 1-I and 1 revealed that iodine migrated from 1-I to 1 through the grain boundary after heating above 398 K. We have succeeded in precisely controlling the iodine content of {Fe(pz)[Pt(CN)4(I) n]} (1-In; n = 0.0-1.0), which resulted in consecutive modulation of Tc in the range 300-400 K while maintaining the hysteresis width. Furthermore, it was demonstrated that iodine migration in the solid mixture was triggered by the spin transition of 1-I. The magnetically bistable porous framework decorating guest interactive open-metal-site in the pore surface makes it possible to modulate Tc ad arbitrium through unique postsynthetic method using iodine migration.

Original languageEnglish
Pages (from-to)8600-8605
Number of pages6
JournalJournal of the American Chemical Society
Volume133
Issue number22
DOIs
Publication statusPublished - Jun 8 2011

All Science Journal Classification (ASJC) codes

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

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