Interestingly, the synergy between the SCO and luminescence property was found not only around the T1/2 values but also in the entire SCO range from 80 K to 300 K, which is rare. The solid-state magnetic susceptibility measurements showed a complete one-step abrupt transition for the complexes 8 and 9 with ~74 K difference in the T1/2 temperature (8 with T1/2 of 129 K and 9 with a T1/2 of 203 K). The average Fe-N bond distances at 100 K were found to be 1.9821 Å and 1.9756 Å, respectively for complexes 8 and 9. At 300 K, the average Fe-N bond distances change to 2.1544 Å and 2.1552 Å, respectively for complexes 8 and 9, suggesting conversion of Fe(II) LS to Fe(II) HS state. The Fe-Nisothiocyanate-C angles for the complexes are larger in the LS state than the HS state, influencing differences in crystal packing as well as intermolecular interactions, thus leading to different magnetic properties.