The effect of halogen functionalization on the spin crossover (SCO) properties of a family of 2-D Hofmann framework materials, [Fe II Pd-(CN) 4 (thioX) 2 ]•2H 2 O (X = Cl and Br; thioCl = (E)-1-(5-chlorothiophen-2-yl)-N-(4H-1,2,4-triazol-4-yl)methanimine) and thioBr = (E)-1-(5-bromothiophen-2-yl)-N-(4H-1,2,4-triazol-4-yl)methanimine)), is reported. Inclusion of both the chloroand bromo-functionalized ligands into the Hofmann-type frameworks (1 Cl •2H 2 O and 2 Br •2H 2 O) results in a blocking of spin-state transitions due to internal chemical pressure effects derived by the collective steric bulk of the halogen atoms and guest molecules. Cooperative one-step SCO transitions are revealed by either guest removal or the application of external physical pressure. Notably, removal of solvent water reveals a robust framework scaffold with only marginal variation between the solvated and desolvated structures (as investigated by powder and single crystal X-ray diffraction). Yet, one-step complete SCO transitions are revealed in 1 Cl and 2 Br with a transition temperature shift between the analogues due to various steric, structural, and electronic considerations. SCO can also be induced in the solvated species, 1 Cl •2H 2 O and 2 Br • 2H 2 O, with the application of physical pressure, revealing a complete one-step SCO transition above 0.62 GPa (as investigated by magnetic susceptibility and single crystal X-ray diffraction measurements).
We probe, here, a family of 2D Hofmann-type frameworks, [FeII(Pd(CN)4)(bztrzX)2]·nH2O [X·nH2O; X = F, Cl, Br; n = 1 (X = Cl, Br) and 3 (X = F); bztrzX = (E)-1-(2-Xphen-1-yl)-N-(4H-1,2,4-triazol-4-yl)methanimine], with halogen-appended ligands. In all cases, there are two crystallographically distinct FeII sites, ({Fe1–Fe2}), driven by the presence of a range of host–host and host–guest interactions. We find that lattice modification through X variation influences the elastic coupling between the FeII sites, the emergence of ferroelastic or antiferroelastic interactions between these sites, and the relative spin-state stabilization/destabilization at each site. In Cl·H2O, the FeII sites show strong elastic coupling, as evidenced by both FeII sites undergoing a spin transition in a single cooperative step, as driven by the volume strain over the high-spin (HS)-to-low-spin (LS) transition. The FeII sites in F·3H2O are also elastically coupled; however, the change of the X atom characteristics and increased guest molecules in the pores result in an antiferroelastic interaction characteristic between Fe1 and Fe2 and a resultant two-step spin-state transition. The change of the X atom to Br in Br·H2O results in the FeII sites being decoupled due to halogen atom steric bulk, resulting in the independent spin-state transition of Fe1 and Fe2 sites and a two-step spin-state transition pathway. Uniquely, all three possible spin-state transition pathways of a two-site switching system are observed in this family [(1) {HS–HS} ↔ {HS–LS} ↔ {LS–LS} for Br·H2O, (2) {HS–HS} ↔ {LS–HS} ↔ {LS–LS} for F·3H2O, and (3) {HS–HS} ↔ {LS–LS} for Cl·H2O for {Fe1–Fe2}]. Overall, these findings broadly support recent theoretical models but highlight that additional structural and topological complexities are needed to form a holistic picture of the drivers of elastic frustration.
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.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.