Fe(III)X tetraphenylporphyrins (X=Br, Cl, I, NCS) usually forms high-spin complexes with S = 5/2 spin ground state. Nevertheless, a spin-state switching phenomenon has been observed by Korszun and Mofat between the five-coordinate high-spin isothiocyanato methaemoglobin and the six-coordinate lowspin histidine ligated isothiocyanato methaemoglobin. Till now, various literature published on the ambidentate thiocyanate ligand ligated Fe(III) tetraphenylporphyrin have shown the electronic and magnetic properties in solution along with their theoretical justification. However, a complete electrochemical study in solution as well as magnetic properties in the solid state have not been investigated so far. Proper justification of the high-spin state of Fe(III) with uniaxial anisotropy in this particular coordination environment is also another area of interest that requires considerable knowledge of the crystal and electronic structure of these mononuclear porphyrins. On the other hand, the modification of the tetraphenylporphyrin ligand by incorporating a methoxy group at the p-position of the aldehyde moiety may lead to a structural phase transition in the system because the methoxy group is known to show change in geometry at different temperatures.