Lattice solvent- and substituent-dependent spin-crossover in isomeric iron(II) complexes.

Spin-state switching in iron(II) complexes composed of ligands featuring moderate ligand-field strength-for example, 2,6-bi(1-pyrazol-1-yl)pyridine (BPP)-is dependent on many factors. Herein, we show that spin-state switching in isomeric iron(II) complexes composed of BPP-based ligands-ethyl 2,6-bis(1-pyrazol-1-yl)isonicotinate (BPP-COOEt, L1) and (2,6-di(1-pyrazol-1-yl)pyridin-4-yl)methylacetate (BPP-CHOCOMe, L2)-is dependent on the nature of the substituent at the BPP skeleton. Bi-stable spin-state switching-with a thermal hysteresis width (Δ) of 44 K and switching temperature () = 298 K in the first cycle-is observed for complex 1·CHCN composed of L1 and BF counter anions. Conversely, the solvent-free isomeric counterpart of 1·CHCN-complex 2a, composed of L2 and BF counter anions-was trapped in the high-spin (HS) state. For one of the polymorphs of complex 2b·CHCN-2b·CHCN-Y, Y denotes yellow colour of the crystals-composed of L2 and ClO counter anions, a gradual and non-hysteretic SCO is observed with = 234 K. Complexes 1·CHCN and 2b·CHCN-Y also underwent light-induced spin-state switching at 5 K due to the light-induced excited spin-state trapping (LIESST) effect. Structures of the low-spin (LS) and HS forms of complex 1·CHCN revealed that spin-state switching goes hand-in-hand with pronounced distortion of the {pyridyl}-Fe-N{pyridyl} angle (), whereas such distortion is not observed for 2b·CHCN-Y. This observation points that distortion is one of the factors making the spin-state switching of 1·CHCN hysteretic in the solid state. The observation of bi-stable spin-state switching with centred at room temperature for 1·CHCN indicates that technologically relevant spin-state switching profiles based on mononuclear iron(II) complexes can be obtained.