In conclusion, we have synthesized and characterized a five-coordinate Fe(III) porphyrin complex with axial thiocyanate acting as a co-ligand. Structural analyses show that the molecule adopts a square pyramidal geometry, and slight distortions are observed with change in temperature. Paramagnetic NMR solution studies follow the Curie law at the measured temperature range. A first order phase transition is observed at 442 K from DSC measurements indicating some structural phase transition in the system at high temperature. Detailed electrochemical and spectroelectrochemical studies in the solution state have been carried out which show the different oxidation and reduction processes, and magnetic measurements highlight the presence of a highly anisotropic ground state, which is supported by crystal structure analyses and Mössbauer spectroscopic measurements at different temperatures. These observations have also been confirmed by using CASSCF/QD-NEVPT2 and DFT calculations which highlight the effect of temperature on the energy gap between the quartet and sextet energy levels that is responsible for the high anisotropy and structural distortions occurring in the system. We believe our studies will provide a different perspective in the field of molecular magnets using porphyrin molecules as viable options.