A family of iron(III) spin crossover complexes with different counteranions, [Fe(qsal-F) − 5, or NCS − 6) have been prepared. All compounds are isostructural and crystallize (triclinic P1̅ space group) with two independent iron(III) centers (Fe1 and Fe2) in the asymmetric unit. No solvent molecules are found in the crystal lattice, allowing us to directly probe the relative influence of anion variation on the spin crossover characteristics. The crystal packing is governed by three types of π−π interactions (type A, type B, and type C), which form undulating 1D chains. Additional interactions (π−F, C−H•••O/F, and P4AE) connect the neighboring chains to form a complex supramolecular network. Hirshfeld surface analysis supports these findings. The anions are located between the cationic [Fe(qsal-F) 2 ] + chains; hence, similar interchain distances (d chain ) are observed irrespective of the anion. However, the interplane distances (d plane ) are influenced by the crystal packing and increase proportionally with the anion size. Magnetic studies reveal that smaller anions tend to stabilize the low-spin state (NO 3 − 3, ClO 4 − 4, and BF 4 − 5), while larger anions (PF 6 − 1 and OTf − 2) exhibit lower transition temperatures (T onset for 1 = 200 K and T for 2 = 190 K) and gradual spin crossovers. The anomaly is 6, where, despite having the smallest anion, it exhibits the lowest transition temperature with magnetic hysteresis in the first step (T 1/2 ↑ = 170 K and T 1/2 ↓ = 157 K). This suggests the size, shape, and supramolecular connectivity of the anion all influence the magnetic properties.
Molecular
devices based on spin-crossover (SCO) compounds are important
targets for molecular electronics. In this study, six air-stable FeIII complexes have been prepared: [Fe(naphBzen)2]Cl (1), [Fe(naphBzen)2]Cl·0.5hexane
(1·0.5hexane); [Fe(naphBzen)2]Cl·2CHCl3·1.15hexane (1·2CHCl3·1.15hexane),
[Fe(naphBzen)2]Br (2), [Fe(naphBzen)2]Br·0.5hexane (2·0.5hexane), and [Fe(naphBzen)2]Br·2CHCl3 (2·2CHCl3). The hexane solvates are isostructural, crystallizing in
the tetragonal space group I41/a. Weak van der Waals interactions between the cations result
in the Fe1 and Fe2 centers packing into chiral chains and exhibiting
two-step SCO. In contrast, the nonisostructural CHCl3 solvates
have a single Fe center and crystallize in the triclinic space group P1̅ and are LS up to 350 K. The solvent-free systems
are also not isostructural with [Fe(naphBzen)2]Cl, crystallizing
in the triclinic space group P1̅, while [Fe(naphBzen)2]Br undergoes a phase transition from tetragonal P43 to P43212 upon
heating from 150 to 280 K. In both cases the compounds are trapped
in the LS state. Magnetic data reveals that SCO occurs only in the
hexane solvates, indicating that even very weak interactions can be
critical in observing spin-crossover behavior.
Metal-organic frameworks (MOFs) is a burgeoning research field and has received increasing interest in recent years due to their inherent advantages of inorganic metal ions, range of organic linkers, tunable...
S1. Synthesis and characterisation S2. Thermogravimetric analysis (TGA) S3. Differential scanning calorimetry (DSC) S4. Powder X-ray diffraction S5. Single crystal X-ray diffraction S6. Magnetic susceptibility S7. Elastic model S8. References S2
S1. Synthesis and characterisation
General ProceduresAll materials were available commercially and used as received (iron(II) perchlorate was handled carefully and in small amounts to avoid any potential explosions). Metal cyanides are toxic and should be used with care and in small amounts.
Spin-crossover is observed for the first time in a FeII(py)3(NC⋯)3 coordination environment which arises in a two-fold interpenetrated 3-D Hofmann-like framework.
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