Tuning the spin-transition properties of pyrene-decorated 2,6-bispyrazolylpyridine based Fe(ii) complexes

Abstract

Two 2,6-bispyrazolylpyridine ligands (bpp) were functionalized with pyrene moieties through linkers of different lengths. In the ligand 2,6-di(1H-pyrazol-1-yl)-4-(pyren-1-yl)pyridine (L1) the pyrene group is directly connected to the bpp moiety via a C–C single bond, while in the ligand 4-(2,6-di(1H-pyrazol-1-yl)pyridin-4-yl)benzyl-4-(pyren-1-yl)butanoate (L2) it is separated by a benzyl ester group involving a flexible butanoic chain. Subsequent complexation of Fe(II) salts revealed dramatic the influence of the nature of the pyrene substitution on the spin-transition behaviour of the resulting complexes. Thus, compound [Fe(L1)2](ClO4)2 (1) is blocked in its high spin state due to constraints caused by a strong intermolecular π–π stacking in its structure. On the other hand, the flexible chain of ligand L2 in compounds [Fe(L2)2](ClO4)2 (2) and [Fe(L2)2](BF4)2·CH3CN·H2O (3) prevents structural constraints allowing for reversible spin transitions. Temperature-dependent studies of the photophysical properties of compound 3 do not reveal any obvious correlation between the fluorescence of the pyrene group and the spin state of the spin transition core.