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The crucial relationship between the spin-crossover (SCO) phenomenon and the crystal lattice can be investigated by tuning the intermolecular interactions of a complex with little change to the electronic environment of the metal. With this aim, the synthesis of the new ligand 2,6-bis[5-(naphth-2-yl)-pyrazol-3-yl]pyridine (H2L) and four different forms ( 1- 4) of the corresponding [Fe(H2L)2]2+ complex cation are presented. H2L exhibits an increased number of aromatic rings with respect to previous analogues to augment the density of π ···π contacts within the system. The four compounds group into three different structural arrangements that coincide with two different SCO behaviour types and a locked high-spin state. The intermolecular interactions that embody the various crystallographic organisations have been analysed through Hirshfeld plots, and the SCO properties of 1- 4 are also discussed in light of the local structural analysis around the FeII centres. [ABSTRACT FROM AUTHOR]

The polypyrazolyl ligand H4L, a functionalised derivative of 3-bpp [bpp = bis(pyrazol-3-yl)pyridine], has been used to synthesise an FeII spin-crossover (SCO) system [Fe(H4L)2](ClO4)2 ·2THF ·H2O ( 1). A subsequent magnetic and structural study revealed that the compound undergoes an incomplete transition with a small hysteresis loop of 8 K and a large residual high spin (HS) fraction. This is consistent with single crystal diffraction results at 250 and 90 K, which show a slight modification of the crystal packing and Fe-N bond lengths. Ageing of the samples leads to more cooperative SCO behaviour, as evidenced by a concomitant increase in the width of the hysteresis loops (reaching up to 20 K) and a decrease in the residual HS fraction at low temperatures. These increases in the bistable domain of the sample, corroborated by measuring the changes in heat capacity through differential scanning calorimetry, are accompanied by a loss of crystallinity, which is attributed to solvent loss and the absorption of atmospheric water. Grinding an aged sample yields a narrower hysteresis loop at higher temperatures. Compound 1 was compared with two previously observed systems of the same family that exhibit different SCO behaviour, [Fe(H4L)2](ClO4)2 ·H2O ·2(CH3)2CO ( 2) and [Fe(H4L)2](ClO4)2 ·2C3H7OH ( 3), by using Hirshfeld surface analysis to have a global view of the intermolecular interactions as enhanced by the functional groups of H4L. [ABSTRACT FROM AUTHOR]