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A Mixed‐Valence {Fe 13 } Cluster Exhibiting Metal‐to‐Metal Charge‐Transfer‐Switched Spin Crossover
Author(s) -
Wen Wen,
Meng YinShan,
Jiao ChengQi,
Liu Qiang,
Zhu HaiLang,
Li YaMing,
Oshio Hiroki,
Liu Tao
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202005998
Subject(s) - valence (chemistry) , spin crossover , chemistry , moiety , metal , crystallography , transition metal , stereochemistry , organic chemistry , catalysis
Abstract It is promising and challenging to manipulate the electronic structures and functions of materials utilizing both metal‐to‐metal charge transfer (MMCT) and spin‐crossover (SCO) to tune the valence and spin states of metal ions. Herein, a metallocyanate building block is used to link with a Fe II ‐triazole moiety and generates a mixed‐valence complex {[(Tp 4‐Me )Fe III (CN) 3 ] 9 [Fe II 4 (trz‐ph) 6 ]}⋅[Ph 3 PMe] 2 ⋅[(Tp 4‐Me )Fe III (CN) 3 ] ( 1 ; trz‐ph=4‐phenyl‐4 H ‐1,2,4‐triazole). Moreover, MMCT occurs between Fe III and one of the Fe II sites after heat treatment, resulting in the generation of a new phase, {[(Tp 4‐Me )Fe II (CN) 3 ][(Tp 4‐Me )Fe III (CN) 3 ] 8 [Fe III Fe II 3 (trz‐ph) 6 ]}⋅ [Ph 3 PMe] 2 ⋅[(Tp 4‐Me )Fe III (CN) 3 ] ( 1 a ). Structural and magnetic studies reveal that MMCT can tune the two‐step SCO behavior of 1 into one‐step SCO behavior of 1 a . Our work demonstrates that the integration of MMCT and SCO can provide a new alternative for manipulating functional spin‐transition materials with accessible multi‐electronic states.