Nakaya Manabu, Kosaka Wataru, Miyasaka Hitoshi, Komatsumaru Yuki, Kawaguchi Shogo, Sugimoto Kunihisa, Zhang Yingjie, Nakamura Masaaki, Lindoy Leonard F, Hayami Shinya
Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1, Kurokami, Chuo-ku, Kumamoto, 860-8555, Japan.
Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 980-8577, Japan.
Angew Chem Int Ed Engl. 2020 Jun 22;59(26):10658-10665. doi: 10.1002/anie.202003811. Epub 2020 Apr 8.
CO -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 (COO-terpy) ]⋅4 H O (1⋅4 H 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 O transformed to solvent-free 1 without loss of porosity by heating to 420 K. Compound 1 exhibited a selective CO adsorption via a gate-open type of the structural modification. Furthermore, the HS/LS transition temperature (T ) was able to be tuned by the CO pressure over a wide temperature range. Unlike 1 exhibits the HS state at 290 K, the CO -accomodated form 1⊃CO (P =110 kPa) was stabilized in the LS state at 290 K, probably caused by a chemical pressure effect by CO accommodation, which provides reversible spin-state conversion by introducing/evacuating CO gas into/from 1.
在一种单核钴(II)配合物中实现了室温下高自旋(HS)和低自旋(LS)态之间对一氧化碳(CO)响应的自旋态转换。一种中性钴(II)配合物[Co(COO-terpy)]·4H₂O(1·4H₂O)通过π-π堆积基序和氢键网络稳定地形成了空腔,从而容纳了四个水分子。通过加热到420 K,结晶态的1·4H₂O转变为无溶剂的1,且孔隙率没有损失。化合物1通过结构修饰的门控开放型表现出对CO的选择性吸附。此外,在很宽的温度范围内,HS/LS转变温度(T)能够通过CO压力进行调节。与1在290 K时呈现HS态不同,CO容纳态的1⊃CO(P₀ = 110 kPa)在290 K时稳定在LS态,这可能是由于CO容纳产生的化学压力效应导致的,通过向1中引入/排出CO气体,可实现可逆的自旋态转换。