Synthesis, Characterization, Reactivity, and Photophysical Studies of Anionic Pincer Ligand-based Metal Complexes

Sarkar, Aniruddha (2024) Synthesis, Characterization, Reactivity, and Photophysical Studies of Anionic Pincer Ligand-based Metal Complexes. PhD thesis, Indian Institute of Science Education and Research Kolkata.

Text (PhD thesis of Aniruddha Sarkar (18RS004)) 18RS004.pdf - Submitted Version Restricted to Repository staff only Download (15MB)

Abstract

This thesis deals with the synthesis, characterization, reactivity, and photophysical studies of different anionic pincer ligand-based systems and their metal complexes. At first, it describes the synthesis of carbene dicarboxamide-based ligand with bulky substituents which allows the formation of monomeric square planar Ni(II) complexes, that have been structurally characterized. Oxidation of these complexes to the high-valent Ni(III) analog, allows the PCET reactions with substituted phenolic (O-H) bond in an oxidative asynchronous fashion. Then it discusses the challenges associated with 1st-row based metal complexes to form long-lived excited states and subsequently describes how the anionic pincer ligand (BIP) can increase the metal-ligand bond covalency to slow down the relaxation of the excited states. This helps increase the lifetime of the excited state of the respective metal complexes. In the end, it describes the synthesis of a tris-carboxamide-based ligand framework which can increase the electron density upon metalation to stabilize the high-valent oxidation state.

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