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CO 2 ‐Induced Spin‐State Switching at Room Temperature in a Monomeric Cobalt(II) Complex with the Porous Nature
Author(s) -
Nakaya Manabu,
Kosaka Wataru,
Miyasaka Hitoshi,
Komatsumaru Yuki,
Kawaguchi Shogo,
Sugimoto Kunihisa,
Zhang Yingjie,
Nakamura Masaaki,
Lindoy Leonard F.,
Hayami Shinya
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202003811
Subject(s) - cobalt , stacking , monomer , spin states , atmospheric temperature range , porosity , molecule , chemistry , crystallography , solvent , hydrogen bond , materials science , inorganic chemistry , thermodynamics , organic chemistry , polymer , physics
CO 2 ‐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 ]⋅4 H 2 O ( 1⋅4 H 2 O ), stably formed cavities generated via π–π stacking motifs and hydrogen bond networks, resulting in the accommodation of four water molecules. Crystalline 1⋅4 H 2 O transformed to solvent‐free 1 without 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 CO 2 pressure over a wide temperature range. Unlike 1 exhibits the HS state at 290 K, the CO 2 ‐accomodated form 1⊃CO 2 ( PCO2=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/from 1 .