TY - JOUR

T1 - Octacyanidorhenate(V) Ion as an Efficient Linker for Hysteretic Two-Step Iron(II) Spin Crossover Switchable by Temperature, Light, and Pressure

AU - Chorazy, Szymon

AU - Charytanowicz, Tomasz

AU - Pinkowicz, Dawid

AU - Wang, Junhao

AU - Nakabayashi, Koji

AU - Klimke, Stephen

AU - Renz, Franz

AU - Ohkoshi, Shin ichi

AU - Sieklucka, Barbara

N1 - Funding Information: This work was financed by the National Science Centre, Poland within the OPUS‐14 project, grant no. 2017/27/B/ST5/00947, and the research grant under the “Diamond Grant” program (DI2018 018148) of the Polish Ministry of Science and Higher Education.

PY - 2020/8/25

Y1 - 2020/8/25

N2 - A two-step hysteretic FeII spin crossover (SCO) effect was achieved in programmed layered Cs{[Fe(3-CNpy)2][Re(CN)8]}⋅H2O (1) (3-CNpy=3-cyanopyridine) assembly consisting of cyanido-bridged FeII-ReV square grid sheets bonded by Cs+ ions. The presence of two non-equivalent FeII sites and the conjunction of 2D bimetallic coordination network with non-covalent interlayer interactions involving Cs+, [ReV(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 FeII state at low temperatures. We prove that octacyanidorhenate(V) ion is an outstanding metalloligand for induction of a cooperative multistep, multiswitchable FeII SCO effect.

AB - A two-step hysteretic FeII spin crossover (SCO) effect was achieved in programmed layered Cs{[Fe(3-CNpy)2][Re(CN)8]}⋅H2O (1) (3-CNpy=3-cyanopyridine) assembly consisting of cyanido-bridged FeII-ReV square grid sheets bonded by Cs+ ions. The presence of two non-equivalent FeII sites and the conjunction of 2D bimetallic coordination network with non-covalent interlayer interactions involving Cs+, [ReV(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 FeII state at low temperatures. We prove that octacyanidorhenate(V) ion is an outstanding metalloligand for induction of a cooperative multistep, multiswitchable FeII SCO effect.

KW - cyanide

KW - framework

KW - iron

KW - rhenium

KW - spin crossover

UR - http://www.scopus.com/inward/record.url?scp=85087299211&partnerID=8YFLogxK

U2 - 10.1002/anie.202007327

DO - 10.1002/anie.202007327

M3 - Article

C2 - 32485003

AN - SCOPUS:85087299211

VL - 59

SP - 15741

EP - 15749

JO - Angewandte Chemie

JF - Angewandte Chemie

SN - 1433-7851

IS - 36

ER -