Two solvent-free mononuclear Fe(III) complexes [Fe(L)(2)]-NO3 (1) and [Fe(L)(2)]ClO4 (2) have been synthesized by employing a new pi-conjugated azo-phenyl substituted ligand, 2-((E)-((2-(ethylamino)ethyl)imino)methyl)-4-(2-phenyldiazenyl)phenol (HL). The noncoordinated azophenyl part of the ligand adopts two different conformations which can exert a varied local distortion around the metal center affecting the spin crossover behavior. The magnetic data (2-450 K) reveal that complex 1 displays spin crossover above room temperature where the ligand is in linear form, while complex 2 shows an incomplete spin transition where the ligand adopts a skew form in the solid state. These complexes represent rare examples of high-temperature spin transition for mononuclear Fe(III) complexes with T-1/2 > 350 K with very high thermal stability. Presence of strong intermolecular interactions and solvent-free nature of the complexes leads to exceptional thermal stability up to 485 K (for 1) and 496 K (for 2) as revealed by thermogravimetric analysis. The magnetic data for complex 1 have been analyzed by employing an Ising-like model with vibrations yielding the enthalpy change Delta H and entropy change Delta S of the spin transition along with the critical temperature T-1/2 and the solid-state cooperativeness Gamma. Spin crossover behavior of complex 1 has also been characterized by differential scanning calorimetry and electron paramagnetic resonance measurements. Ab initio calculations have been performed to analyze the difference in energies of the ground state and excited states of the complexes.