1. Spin-Crossover 2-D Hofmann Frameworks Incorporating an Amide-Functionalized Ligand: N-(pyridin-4-yl)benzamide
- Author
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Ong, X, Ahmed, M, Xu, L, Brennan, AT, Hua, C, Zenere, KA, Xie, Z, Kepert, CJ, Powell, BJ, Neville, SM, Ong, X, Ahmed, M, Xu, L, Brennan, AT, Hua, C, Zenere, KA, Xie, Z, Kepert, CJ, Powell, BJ, and Neville, SM
- Abstract
Two analogous 2-D Hofmann-type frameworks, which incorporate the novel ligand N-(pyridin-4-yl)benzamide (benpy) [FeII(benpy)2M(CN)4]·2H2O (M = Pd (Pd(benpy)) and Pt (Pt(benpy))) are reported. The benpy ligand was explored to facilitate spin-crossover (SCO) cooperativity via amide group hydrogen bonding. Structural analyses of the 2-D Hofmann frameworks revealed benpy-guest hydrogen bonding and benpy-benpy aromatic contacts. Both analogues exhibited single-step hysteretic spin-crossover (SCO) transitions, with the metal-cyanide linker (M = Pd or Pt) impacting the SCO spin-state transition temperature and hysteresis loop width (Pd(benpy): T½↓↑: 201, 218 K, ∆T: 17 K and Pt(benpy): T½↓↑: 206, 226 K, ∆T: 20 K). The parallel structural and SCO changes over the high-spin to low-spin transition were investigated using variable-temperature, single-crystal, and powder X-ray diffraction, Raman spectroscopy, and differential scanning calorimetry. These studies indicated that the ligand–guest interactions facilitated by the amide group acted to support the cooperative spin-state transitions displayed by these two Hofmann-type frameworks, providing further insight into cooperativity and structure–property relationships.
- Published
- 2021