Citation: Yan-Rui LEI, Hai-Lang ZHU, Jie HUANG, Ren-He ZHOU, Tao LIU. Structure and magnetism of cyanide-bridged [FeCo]-based chain-like complexes[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(10): 1969-1979. doi: 10.11862/CJIC.2023.147 shu

Structure and magnetism of cyanide-bridged [FeCo]-based chain-like complexes

State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, Dalian University of Technology, Dalian, Liaoning 116024, China

Corresponding author: Tao LIU, liutao@dlut.edu.cn
Received Date: 28 March 2023
Revised Date: 5 June 2023

Figures(7)

We report two cyanide-bridged mixed-valence chain-like coordination polymers by the self-assembly reaction of tricyanoferrate(Ⅲ) building blocks (Bu₄N)[Fe(PzTp)(CN)₃] (PzTp=tetrakis(pyrazolyl)borate) and Co(Ⅱ) ions in the presence of monodentate ligand (E)-1-styryl-1H-imidazole (Bzi). X-ray diffraction analysis indicated that complex [Fe(PzTp)(CN)₃]₂[Co(Bzi)₄]₂(ClO₄)₂·H₂O (1) adopts a square-wave type chain structure, while complex [Fe(PzTp) (CN)₃]₂[Co(Bzi)₂]·CH₃OH (2) forms double zigzag chains that contain methanol solvent molecules. Magnetic studies revealed that complex 1 displayed a thermally induced spin transition at around 360 K, while complex 2 exhibited a solvent-induced two-step spin transition at approximately 200 K. Variable-temperature infrared spectra confirmed the thermally induced intermetallic charge transfer behavior. Additionally, photomagnetic experiments revealed that complex 1 displayed reversible light-induced charge transfer behavior when alternately irradiated with 808 and 532 nm light, while the charge transfer behavior of complex 2 could be induced by 808 nm irradiation. The magneto-structural relationship analysis indicates that the different hydrogen bonding interactions and local coordination environments of the cobalt sites in complexes 1 and 2 are the main factors contributing to their distinct charge transfer and light-responsive properties.
- intermetallic charge transfer,
- tricyanometallate,
- cyanide-bridged,
- coordination polymer
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