4.8 Article

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

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 59, Issue 26, Pages 10658-10665

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202003811

Keywords

carbon dioxide; cobalt(II) ions; hydrogen bonding; pi-pi stacking; spin-state change

Funding

  1. Ministry of Education, Culture, Sports, Science, and Technology, Japan [JP17H01200, 16H02269, 18K19050, 15H05208, 18K05055]
  2. Japan Society for the Promotion of Science [17H05137]
  3. E-IMR project
  4. Cooperative Research Program of Network Joint Research Centre for Materials and Devices
  5. Grants-in-Aid for Scientific Research [17H05137, 15H05208] Funding Source: KAKEN

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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, [Co-II(COO-terpy)(2)]center dot 4 H2O (1 center dot 4 H2O), stably formed cavities generated via pi-pi stacking motifs and hydrogen bond networks, resulting in the accommodation of four water molecules. Crystalline 1 center dot 4 H2O transformed to solvent-free1without loss of porosity by heating to 420 K. Compound 1 exhibited a selective CO(2)adsorption via a gate-open type of the structural modification. Furthermore, the HS/LS transition temperature (T-1/2) 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 superset of CO2(P-CO2=110 kPa) was stabilized in the LS state at 290 K, probably caused by a chemical pressure effect by CO(2)accommodation, which provides reversible spin-state conversion by introducing/evacuating CO(2)gas into/from1.

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