To look for the correlation between luminescence and SCO in 2, temperature-dependent PL measurements were performed between 10 and 300 K in solid-state for both ligand L2 and complex 2. At room temperature, PL spectra displayed an emission band at 516 and 513 nm for L2 and 2, respectively under excitation at 380 nm, suggesting retention of the PL properties of the ligand upon coordination with iron(II) center. The variable temperature PL spectra displayed distinct temperature-dependent emission characteristics for L2 and 2. Upon cooling, the emission intensity of L2 increased slowly due to suppression of thermal quenching, while for 2, the emission intensity initially decreased upon cooling down to the lowest value at 250 K and then gradually increased to reach a maximum at 10 K. The appearance of the abnormal behavior of the emission intensity in the SCO region confirmed the synergic relation between SCO and luminescence in 2.