LI, Xiang; ZHANG, Dong; QIAN, Yuqing; LIU, Wenxuan; MATHONIÈRE, Corine; CLÉRAC, Rodolphe; BAO, Xin

doi:10.1021/jacs.2c13697

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LI, Xiang
Nanjing University of Science and Technology [NJUST]

ZHANG, Dong
Nanjing University of Science and Technology [NJUST]

QIAN, Yuqing
Nanjing University of Science and Technology [NJUST]

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Journal of the American Chemical Society. 2023, vol. 145, n° 17, p. 9564-9570

American Chemical Society

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In 2019, our groups described a unique Fe II complex, [Fe(2Me L)(NCBH 3) 2 ] (2Me L = N,N'-dimethyl-N,N'-bis-(2-pyridylmethyl)-1,2-ethanediamine) possessing a low-spin ground state that is not easily accessible due to the extremely slow dynamics of the high-spin to low-spin phase transition. Herein, we report the successful chemical manipulation of this spin-crossover (SCO) process through controlled metal-ion dilutions. The emergence or suppression of the thermally induced SCO behavior was observed depending on the radius of the metal ion used for the dilution (Ni II or Zn II). Reversible photo-switching has been confirmed in all mixed-metal complexes whether the lowspin state is thermally accessible. Remarkably, the dilution with Zn II metal ions stabilizes HS Fe II complexes with complete suppression of the thermally induced SCO process without destroying the reversible photoswitchability of the material.< Réduire

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Chemical Manipulation of the Spin-Crossover Dynamics through Judicious Metal-Ion Dilution

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