SYNTHESIS, STRUCTURAL CHARACTERIZATION AND DFT CALCULATIONS OF meta-BENZIPORPHODIMETHENES AND THEIR METAL COMPLEXES

Abstract

Thorough review of meta-benziporphodimethene analogues and their metal complexes is presented in this thesis. Foundation of research gap was laid through exhaustive literature review. The focus of the research was then directed to identifying the factors that could improve the stability of the free base meta benziporphodimethene analogues. Synthesis of sterically hindered analogues of meta benziporphodimethene and its cadmium and mercury complexes have been discussed in Chapter 3 of this thesis. UV-Vis, 1H-NMR and mass spectrometry was used to confirm the synthesis of different analogues. Then we moved to determine the structural features that lead to thermodynamically stable moieties, various tautomer have been analysed computationally, which were obtained either by shuffling N confused pyrrole subunits, oxygenated pyrrole subunit (both O-up and O-down), position of hydrogen on inner nitrogen atom of pyrrole or replacing pyrrolic nitrogen with a heteroatom. Further, the intramolecular hydrogen bond energies have been determined using a Molecular Tailoring approach (MTA), viz. Chapter 4 of this thesis. The X-ray solid state structures affirmed the presence of two conformers of meta benziporphodimethene viz. syn and anti.