Spin-Crossover 2-D Hofmann Frameworks Incorporating an Amide-Functionalized Ligand: N-(pyridin-4-yl)benzamide

Two analogous 2-D Hofmann-type frameworks, which incorporate the novel ligand N-(pyridin-4-yl)benzamide (benpy) [Fe-II(benpy)(2)M(CN)(4)].2H(2)O (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): T-1/2 down arrow up arrow: 201, 218 K, T: 17 K and Pt(benpy): T-1/2 down arrow up arrow: 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.

Automated summary

Two analogous 2-D Hofmann-type frameworks incorporating the ligand benpy were studied for their spin-crossover cooperativity via hydrogen bonding. Structural analyses revealed interactions between benpy and guest molecules, as well as benpy-benpy aromatic contacts. Investigations into the impact of the metal-cyanide linker on spin-state transitions and hysteresis loops provided insights into cooperativity and structure-property relationships.