期刊
INORGANIC CHEMISTRY
卷 61, 期 30, 页码 11667-11674出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.2c01253
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资金
- Australian Research Council (ARC) [LE170100144]
- ARC
- Australian Research Council [LE170100144] Funding Source: Australian Research Council
This study presents a detailed analysis of the structure and spin-crossover effects of a two-dimensional (2-D) Hofmann-like framework [Fe(furpy)(2)Pd(CN)(4)]center dot nG. The inclusion of guest modifications, particularly ethanol, affects the framework communication and local structure, leading to changes in the spin-state transition mechanism.
A detailed study of the two-dimensional (2-D) Hofmann-like framework [Fe(furpy)(2)Pd(CN)(4)]center dot nG (furpy: N-(pyridin-4-yl)furan-2-carboxamide, G = H2O,EtOH (A center dot H2O,Et), and H2O (A center dot H2O)) is presented, including the structural and spin-crossover (SCO) implications of subtle guest modification. This 2-D framework is characterized by undulating Hofmann layers and an array of interlayer spacing environments-this is a strategic approach that we achieve by the inclusion of a ligand with multiple host-host and host-guest interaction sites. Variable-temperature magnetic susceptibility studies reveal an asymmetric multistep SCO for A center dot H2O,Et and an abrupt single-step SCO for A center dot H2O with an upshift in transition temperature of similar to 75 K. Single-crystal analyses show a primitive orthorhombic symmetry for A center dot H2O,Et characterized by a unique Fe-II center-the multistep SCO character is attributed to local ligand orientation. Counterintuitively, A center dot H2O shows a triclinic symmetry with two inequivalent Fe-II centers that undergo a cooperative single-step high-spin (HS)-to-low-spin (LS) transition. We conduct detailed structure-function analyses to understand how the guest ethanol influences the delicate balance between framework communication and, therefore, the local structure and spill-state transition mechanism.
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