Thermal and light-induced spin-transitions in iron(II) complexes of 2,6-bis(4-halopyrazolyl)pyridines: the influence of polymorphism on a spin-crossover compound

The syntheses of 2,6-bis(4-chloropyrazol-1-yl)pyridine (L-1), 2,6-bis(4-bromopyrazol-1-yl)pyridine (L-2) and 2,6-bis(4-iodopyrazol-1-yl)pyridine (L-3) by electrophilic halogenation of 2,6-bis(pyrazol-1-yl)pyridine are reported. The complex [Fe(L-1)(2)][BF4](2) crystallises in two different solvent-free polymorphs. The tetragonal (alpha) form crystallises in a known version of the terpyridine embrace structure, and undergoes an abrupt spin-transition at 202 K. The orthorhombic (beta) form exhibits a modified form of the same packing motif, containing two unique iron sites in a 2 : 1 ratio. One-third of the complex molecules in that material undergo a very gradual thermal spin-crossover centred at 137 K. Comparison of the two structures implies that spin-crossover cooperativity in the alpha-polymorph is transmitted in two dimensions within the extended lattice. [Fe(L-2)(2)][BF4](2) is isostructural with alpha-[Fe(L-1)(2)][BF4](2) and exhibits a similarly abrupt spin-transition at 253 K. In contrast, [Fe(L-3)(2)][BF4](2) is low-spin as a powder at 360 K and below and can be crystallised as two different solvates from acetone solution. All three compounds exhibit the LIESST effect at 10 K, with photoconversions of 40-100%. Their LIESST relaxation temperatures obey the empirical T(LIESST) = T-0 - 0.3 T-1/2 (T-0 = 150 K) law that we have previously proposed for this class of compound.