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The effect of porphyrin macrocycle size on the stability of porphyrin organometallic complexes in their solid state, under different heating conditions, has been studied. UV-vis spectroscopy has been used to monitor the structural and spectroscopic changes that occur in the porphyrin macrocycle upon heating to determine the thermal decomposition processes that proceed in the solid state. Using porphyrin Zn(porphyrin), H(2)O molecules and benzene as model systems, we have explored the type of bonding between the porphyrin macrocycles and the solid-state substrates. The result is a clear correlation between the stability of the porphyrin macrocycle in its solid state and its macrocycle size. The presence of aromatic macrocycles and weak hydrogen bonding in the solid state results in reduced stability of the porphyrin macrocycles in their solid state. On the other hand, the relative stability