Halogen-Substituted Spin-Crossover Fe(III) Compounds with Photoresponsive Properties.

Halogen-substituted Fe(III) compounds, [Fe(HphsalpmX)2]PTFB (HphsalpmX = 5-X-(R,S)-((phenyl(2-pyridyl)methylimino)methyl)phenol, PTFB = phenyltrifluoroborate; X = F for 1, Cl for 2, Br for 3) and [Fe(HphsalpmX)2]PTFB·MeOH (X = I for 4·MeOH), were synthesized. Compounds 1, 4·MeOH, and its desolvated form 4 exhibited an invariant high-spin state in the whole temperature range, while 2 and 3 underwent gradual, nonhysteretic, and incomplete spin crossover (SCO) with transition temperatures (TC) of 153 and 220 K, respectively. Interestingly, the SCO-active compounds 2 and 3 showed light-induced excited spin-state trapping (LIESST) effects at 10 K, and light-induced reversible ON/OFF switching behaviors were realized by alternately using 880 and 1064 nm light, while the thermally inert compound 4·MeOH unexpectedly showed a reverse-LIESST effect. These results may help to design and synthesize new photoresponsive SCO Fe(III) compounds for the development of switchable materials.