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

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 L¹ and L², featuring OPE-type backbone end-capped with metal coordinating BPP were designed and synthetized. The ligand L² 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 L¹. Solution phase complexation of L¹ and L² with Fe(BF₄)₂·6H₂O resulted in the formation of insoluble materials of the composition [Fe(L¹)] _n (BF₄)_2n and [Fe(L²)] _n (BF₄)_2n as inferred from elemental analyses. Complex [Fe(L¹)] _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(L²)] _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(L¹)] _n (BF₄)_2n revealed the presence of nm-sized crystallites implying a possible methodology towards the template-free synthesis of functional-SCO nanostructures.