Solvent-Induced Polymorphism of Iron(II) Spin Crossover Complexes

Two new mononuclear iron(II) compounds (1) and (2) of the general formula [Fe(L) $_{2}$](BF$_{4}$)$_{2}$·nCH$_{3}$CN (L = 4-(2-bromoethyn-1-yl)-2,6-bis(pyrazol-1-yl)pyridine, n = 1 for (1) and n = 2 for compound (2)), were synthesized. The room temperature crystallization afforded concomitant formation of two different solvent analogues: compound (1) exhibiting triclinic P-1 and compound (2) monoclinic C2/c symmetry. Single-crystal X-ray studies confirmed the presence of the LS (low-spin) state for both compounds at 180 K and of the HS (high-spin) state for compound (2) at 293 K, in full agreement with the magnetic investigations for both solvent polymorphs. Compound (1) exhibits spin transition above 293 K followed by subsequent solvent liberation, while the spin transition of (2) takes already place at 237 K. After complete solvent removal from the crystal lattice, compound (1d) (the desolvated polymorph derived from (1)) exhibits spin transition centered at 342 K accompanied by a thermal hysteresis loop, while the analogous compound (2d) (the desolvated derivate of compound (2)) remains blocked in the HS state over all the investigated temperature range

Spin-crossover in iron(II)-phenylene ethynylene-2,6-di(pyrazol-1-yl) pyridine hybrids: toward switchable molecular wire-like architectures

Luminescent oligo(p-phenylene ethynylene) (OPE) and spin-crossover (SCO) active Fe(II)2,6-di(pyrazol-1-yl) pyridine (BPP) systems are prominent examples proposed to develop functional materials such as molecular wires/memories. A marriage between OPE and Fe(II)-BPP systems is a strategy to obtain supramolecular luminescent ligands capable of metal coordination useful to produce novel spin-switchable hybrids with synergistic coupling between spin-state of Fe(II) and a physical property associated with the OPE skeleton, for example, electronic conductivity or luminescence. To begin in this direction, two novel ditopic ligands, namely L-1 and L-2, featuring OPE-type backbone end-capped with metal coordinating BPP were designed and synthetized. The ligand L-2 tailored with 2-ethylhexyloxy chains at the 2 and 5 positions of the OPE skeleton shows modulated optical properties and improved solubility in common organic solvents relative to the parent ligand L-1. Solution phase complexation of L-1 and L-2 with Fe(BF4)(2)center dot 6H(2)O resulted in the formation of insoluble materials of the composition [Fe(L-1)](n)(BF4)(2n) and [Fe(L-2)](n)(BF4)(2n) as inferred from elemental analyses. Complex [Fe(L-1)](n)(BF4)(2n) underwent thermal SCO centred at T-1/2 = 275 K as well as photoinduced low-spin to high-spin transition with the existence of the metastable high-spin state up to 52 K. On the other hand, complex [Fe(L-2)]n(BF4)(2n), tethered with 2-ethylhexyloxy groups, showed gradual and half-complete SCO with 50% of the Fe(II)-centres permanently blocked in the high-spin state due to intermolecular steric interactions. The small angle x-ray scattering (SAXS) pattern of the as-prepared solid complex [Fe(L-1)](n)(BF4)(2n) revealed the presence of nm-sized crystallites implying a possible methodology towards the template-free synthesis of functional-SCO nanostructures

Spin-crossover in iron(II)-phenylene ethynylene-2,6-di(pyrazol-1-yl) pyridine hybrids: toward switchable molecular wire-like architectures

Luminescent oligo(p-phenylene ethynylene) (OPE) and spin-crossover (SCO) active Fe(II)2,6-di(pyrazol-1-yl) pyridine (BPP) systems are prominent examples proposed to develop functional materials such as molecular wires/memories. A marriage between OPE and Fe(II)-BPP systems is a strategy to obtain supramolecular luminescent ligands capable of metal coordination useful to produce novel spin-switchable hybrids with synergistic coupling between spin-state of Fe(II) and a physical property associated with the OPE skeleton, for example, electronic conductivity or luminescence. To begin in this direction, two novel ditopic ligands, namely L-1 and L-2, featuring OPE-type backbone end-capped with metal coordinating BPP were designed and synthetized. The ligand L-2 tailored with 2-ethylhexyloxy chains at the 2 and 5 positions of the OPE skeleton shows modulated optical properties and improved solubility in common organic solvents relative to the parent ligand L-1. Solution phase complexation of L-1 and L-2 with Fe(BF4)(2)center dot 6H(2)O resulted in the formation of insoluble materials of the composition [Fe(L-1)](n)(BF4)(2n) and [Fe(L-2)](n)(BF4)(2n) as inferred from elemental analyses. Complex [Fe(L-1)](n)(BF4)(2n) underwent thermal SCO centred at T-1/2 = 275 K as well as photoinduced low-spin to high-spin transition with the existence of the metastable high-spin state up to 52 K. On the other hand, complex [Fe(L-2)]n(BF4)(2n), tethered with 2-ethylhexyloxy groups, showed gradual and half-complete SCO with 50% of the Fe(II)-centres permanently blocked in the high-spin state due to intermolecular steric interactions. The small angle x-ray scattering (SAXS) pattern of the as-prepared solid complex [Fe(L-1)](n)(BF4)(2n) revealed the presence of nm-sized crystallites implying a possible methodology towards the template-free synthesis of functional-SCO nanostructures