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A 2D coordination polymer, [Fe(L)2(NCSe)2]·6MeOH·14H2O n (1; L = 2,5-dipyridylethynylene-3,4-ethylenedioxythiophene), has been synthesized based on a redox active luminescence ligand. 1 possesses a 2D [4 × 4] square-grid network where the iron(II) center is in a FeN6 octahedral coordination environment. 1 displays reversible thermoinduced high-spin (HS; S = 2) to diamagnetic low-spin (LS; S = ON/OFF spin-state switching with a T1/2 value of 150 K. Interestingly, optical reflectivity and photomagnetic studies at 10 K under light irradia