The detailed 1 H and 13 C NMR analysis of 5,10,19,24-tetramesityl-33,35,36,38,39-pentathiaheptaphyrin (1) and 5,10,19,24-tetraphenyl-35,36-dioxa-33,38,39-trithiaheptaphyrin (2) in the native and protonated state were carried out using two-dimensional NMR techniques. The analysis suggests that the earlier reported structure containing inverted terminal thiophene of trithiophene should be corrected as the inverted thiophene and furan of bithiophene and bifuran instead of trithiophene system of 1 and 2, respectively. Temperature dependent and titration studies suggest that 1 is less flexible in the native state then 2 due to presence of the mesityl group despite having disorder due to the presence of the heavier sulphur atom. This was consequently proven by the NMR information obtained in 5,10,19,24-tetramesityl-35,36-dioxa-33,38,39-trithiaheptaphyrin (3). Whereas in its protonated state, 2 was found to be less flexible than 1 due to presence of intramolecular hydrogen bonding involving N - H --- O between the pyrrole NH and oxygen of the furan of bifuran system. A systematic NMR strategy has been generated in order to provide complete a structure determination of expanded porphyrins along with their dynamic behavior.