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Article

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

1
The School of Chemistry, The University of New South Wales, Sydney 2052, Australia
2
School of Chemistry, The University of Melbourne, Parkville 3010, Australia
3
The School of Chemistry, The University of Sydney, Sydney 2006, Australia
4
School of Mathematics and Physics, The University of Queensland, St. Lucia 4072, Australia
*
Author to whom correspondence should be addressed.
Received: 14 December 2020 / Revised: 17 February 2021 / Accepted: 20 February 2021 / Published: 1 March 2021
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. View Full-Text
Keywords: spin crossover; Hofmann framework; hydrogen bonding spin crossover; Hofmann framework; hydrogen bonding
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MDPI and ACS Style

Ong, X.; Ahmed, M.; Xu, L.; Brennan, A.T.; Hua, C.; Zenere, K.A.; Xie, Z.; Kepert, C.J.; Powell, B.J.; Neville, S.M. Spin-Crossover 2-D Hofmann Frameworks Incorporating an Amide-Functionalized Ligand: N-(pyridin-4-yl)benzamide. Chemistry 2021, 3, 360-372. https://0-doi-org.brum.beds.ac.uk/10.3390/chemistry3010026

AMA Style

Ong X, Ahmed M, Xu L, Brennan AT, Hua C, Zenere KA, Xie Z, Kepert CJ, Powell BJ, Neville SM. Spin-Crossover 2-D Hofmann Frameworks Incorporating an Amide-Functionalized Ligand: N-(pyridin-4-yl)benzamide. Chemistry. 2021; 3(1):360-372. https://0-doi-org.brum.beds.ac.uk/10.3390/chemistry3010026

Chicago/Turabian Style

Ong, Xandria, Manan Ahmed, Luonan Xu, Ashley T. Brennan, Carol Hua, Katrina A. Zenere, Zixi Xie, Cameron J. Kepert, Benjamin J. Powell, and Suzanne M. Neville 2021. "Spin-Crossover 2-D Hofmann Frameworks Incorporating an Amide-Functionalized Ligand: N-(pyridin-4-yl)benzamide" Chemistry 3, no. 1: 360-372. https://0-doi-org.brum.beds.ac.uk/10.3390/chemistry3010026

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