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Octacyanidorhenate(V) Ion as an Efficient Linker for Hysteretic Two‐Step Iron(II) Spin Crossover Switchable by Temperature, Light, and Pressure
Author(s) -
Chorazy Szymon,
Charytanowicz Tomasz,
Pinkowicz Dawid,
Wang Junhao,
Nakabayashi Koji,
Klimke Stephen,
Renz Franz,
Ohkoshi Shinichi,
Sieklucka Barbara
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.202007327
Subject(s) - spin crossover , ion , bimetallic strip , cooperativity , chemistry , spin transition , covalent bond , hysteresis , spin states , irradiation , crystallography , materials science , inorganic chemistry , condensed matter physics , metal , physics , organic chemistry , biochemistry , nuclear physics
Abstract A two‐step hysteretic Fe II spin crossover (SCO) effect was achieved in programmed layered Cs{[Fe(3‐CNpy) 2 ][Re(CN) 8 ]}⋅H 2 O ( 1 ) (3‐CNpy=3‐cyanopyridine) assembly consisting of cyanido‐bridged Fe II ‐Re V square grid sheets bonded by Cs + ions. The presence of two non‐equivalent Fe II sites and the conjunction of 2D bimetallic coordination network with non‐covalent interlayer interactions involving Cs + , [Re V (CN) 8 ] 3− ions, and 3‐CNpy ligands, leads to the occurrence of two steps of thermal SCO with strong cooperativity giving a double thermal hysteresis loop. The resulting spin‐transition phenomenon could be tuned by an external pressure giving the room‐temperature range of SCO, as well as by visible‐light irradiation, inducing an efficient recovery of the high‐spin Fe II state at low temperatures. We prove that octacyanidorhenate(V) ion is an outstanding metalloligand for induction of a cooperative multistep, multiswitchable Fe II SCO effect.