Thermo- and photoinduced spin state switching in an iron(II) 2D coordination network associated with large light-induced thermal hysteresis and tuning of dimensionality via ligand modulation

Three iron(II) complexes, [Fe(L1)(2)(NCS)(2)(MeOH)(2)] (1), [Fe(L1)(2)(NCSe)(2)(MeOH)(2)] (2), and [Fe(L2)(2)(NCS)(2)](n) (3) (L1 = 2,5-dipyridyl-3,4-ethylenedioxythiophene and L2 = 2,5-diethynylpyridinyl-3,4-ethylenedioxythiophene), have been synthesized using redox-active luminescent ethylenedioxythiophene (EDOT)-based ligands, and characterized by variable temperature single-crystal X-ray diffraction, (photo)magnetic, optical reflectivity, and spectroscopy studies. Magneto-structural investigations revealed that 1 and 2 are mononuclear with a FeN4O2 octahedral coordination geometry and remain in a high-spin (HS) (S = 2) state in a temperature range of 2-280 K. Interestingly, a 2D coordination network structure with FeN6 surrounding each iron center was observed for 3, which exhibits reversible thermo-induced spin-state switching between the paramagnetic high-spin (HS) (S = 2) and diamagnetic low-spin (LS) (S = 0) states at around 105 K (T-1/2). Furthermore, optical reflectivity and photomagnetic measurements at low temperature confirmed that 3 shows reversible ON/OFF switching between the photoinduced excited paramagnetic HS metastable state and diamagnetic LS state under light irradiation (ON mode using red light and OFF mode using green light). Finally, the photoinduced excited HS state can be reversibly relaxed back to the diamagnetic ground LS state by heating the system at ca. 88 K (T-LIESST = 88 K) (light-induced excited spin state trapping (LIESST) effect). Furthermore, 3 also showed an exciting and unique 18 K wide light-induced thermal hysteresis (LITH) effect above liquid nitrogen temperature (100 K). DFT and CASSCF level theoretical calculations were utilized to better understand the magneto-structural correlations of these complexes.

Automated summary

Three iron(II) complexes with redox-active luminescent ethylenedioxythiophene (EDOT)-based ligands were synthesized and characterized through various analyses. The complexes exhibit intriguing magnetic and photoresponsive properties, including reversible spin-state switching and light-induced thermal hysteresis effects, showing unique and temperature-sensitive behavior.