In this work we have synthesized the isothiocyanato ligated five coordinated square pyramidal Fe(III) tetraphenylporphyrin complex FeTMPP(NCS).CH3CN (1) and have explored the structural, electronic, electrochemical, spectroelectrochemical and magnetic properties and have also explained these properties by theoretical calculations and modelling (H2TMPP = p-methoxytetraphenylporphyrin), in attempts to realize their suitable candidature for molecular magnetic systems . Crystal Structures Analyses. Single crystal X-ray structure analyses were carried out on a suitable single crystal of 1 at 100 K, 250 K, and 295 K (Table -3), where 1 crystallized in monoclinic space group P 21/n (Z=4). The asymmetric unit (Figure ) at all the measured temperatures contains the five-coordinate thiocyanato ligated to the iron porphyrin complex along with one acetonitrile molecule, which appears as solvent of crystallization. The iron centre is bonded to four donor pyrrole nitrogen atoms from the porphyrin moiety and at the axial position to the N end of the ambidentate thiocyanate ligand, adopting a spherical square pyramidal geometry at all the temperatures as determined from continuous shape measures (CShM)