CO2-Induced Spin-State Switching at Room Temperature in a Monomeric Cobalt(II) Complex with the Porous Nature

Manabu Nakaya, Wataru Kosaka, Hitoshi Miyasaka, Yuki Komatsumaru, Shogo Kawaguchi, Kunihisa Sugimoto, Yingjie Zhang, Masaaki Nakamura, Leonard F. Lindoy, Shinya Hayami

Research output: Contribution to journalArticlepeer-review

10 Citations (Scopus)

Abstract

CO2-responsive spin-state conversion between high-spin (HS) and low-spin (LS) states at room temperature was achieved in a monomeric cobalt(II) complex. A neutral cobalt(II) complex, [CoII(COO-terpy)2]⋅4 H2O (1⋅4 H2O), stably formed cavities generated via π–π stacking motifs and hydrogen bond networks, resulting in the accommodation of four water molecules. Crystalline 1⋅4 H2O transformed to solvent-free 1 without loss of porosity by heating to 420 K. Compound 1 exhibited a selective CO2 adsorption via a gate-open type of the structural modification. Furthermore, the HS/LS transition temperature (T1/2) was able to be tuned by the CO2 pressure over a wide temperature range. Unlike 1 exhibits the HS state at 290 K, the CO2-accomodated form 1⊃CO2 (P (Formula presented.) =110 kPa) was stabilized in the LS state at 290 K, probably caused by a chemical pressure effect by CO2 accommodation, which provides reversible spin-state conversion by introducing/evacuating CO2 gas into/from 1.

Original languageEnglish
Pages (from-to)10658-10665
Number of pages8
JournalAngewandte Chemie - International Edition
Volume59
Issue number26
DOIs
Publication statusPublished - 2020 Jun 22

Keywords

  • carbon dioxide
  • cobalt(II) ions
  • hydrogen bonding
  • spin-state change
  • π–π stacking

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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