Optimization of crystal packing in semiconducting spin-crossover materials with fractionally charged TCNQ δ- anions (0 < δ < 1).

Co-crystallization of the prominent Fe(ii) spin-crossover (SCO) cation, [Fe(3-bpp)2]2+ (3-bpp = 2,6-bis(pyrazol-3-yl)pyridine), with a fractionally charged TCNQ δ- radical anion has afforded a hybrid complex [Fe(3-bpp)2](TCNQ)3·5MeCN (1·5MeCN, where δ = -0.67). The partially desolvated material shows semiconducting behavior, with the room temperature conductivity σ RT = 3.1 × 10-3 S cm-1, and weak modulation of conducting properties in the region of the spin transition. The complete desolvation, however, results in the loss of hysteretic behavior and a very gradual SCO that spans the temperature range of 200 K. A related complex with integer-charged TCNQ- anions, [Fe(3-bpp)2](TCNQ)2·3MeCN (2·3MeCN), readily loses the interstitial solvent to afford desolvated complex 2 that undergoes an abrupt and hysteretic spin transition centered at 106 K, with an 11 K thermal hysteresis. Complex 2 also exhibits a temperature-induced excited spin-state trapping (TIESST) effect, upon which a metastable high-spin state is trapped by flash-cooling from room temperature to 10 K. Heating above 85 K restores the ground-state low-spin configuration. An approach to improve the structural stability of such complexes is demonstrated by using a related ligand 2,6-bis(benzimidazol-2'-yl)pyridine (bzimpy) to obtain [Fe(bzimpy)2](TCNQ)6·2Me2CO (4) and [Fe(bzimpy)2](TCNQ)5·5MeCN (5), both of which exist as LS complexes up to 400 K and exhibit semiconducting behavior, with σ RT = 9.1 × 10-2 S cm-1 and 1.8 × 10-3 S cm-1, respectively.