Phenalenyl-Based Molecules in Metal-free Photocatalysis

Datta, Paramita (2025) Phenalenyl-Based Molecules in Metal-free Photocatalysis. PhD thesis, Indian Institute of Science Education and Research Kolkata.

Text (PhD thesis of Paramita Datta (18RS058)) 18RS058.pdf - Submitted Version Restricted to Repository staff only Download (56MB)

Abstract

The research works presented in this PhD thesis entitled “Phenalenyl-Based Molecules in Metal-free Photocatalysis” discusses the utilization of polycyclic odd alternant hydrocarbon phenalenyl (PLY) systems in designing efficient photocatalysts for various organic transformations (including gas activation) taking advantage of the energetically accessible non-bonding molecular orbital (NBMO) under photoirradiation as a metal-free catalyst. This thesis is divided into three chapters. The first is “Introduction”, which discusses a general overview of photocatalysis and its application in organic chemistry. The later section describes the properties of phenalenyl-based molecules with the early approaches, giving a logical explanation for designing a phenalenyl-based catalytic system. The second chapter, “Results and Discussion”, is subdivided into three sections that describe the dissertation work carried out during the PhD tenure. Section 2.1 describes the photoinduced generation of phenalenyl-based radical species supported by detailed spectroscopic studies and its application in the development of redox catalysis for reductive C-C coupling reactions such as reductive pinacol coupling and reductive alkylation of terminal aryl alkynes with aliphatic halides to obtain Z-selective olefins. Section 2.2 discusses the first metal-free photo-divergent synthetic routes to anti-Markovnikov hydroalkylation and cyclopropanation of styrenes using diazoacetates, in which the diazoacetate serves as a carbene precursor. In the 2.3 section, a highly efficient, one-step method for SO2 functionalization under visible light, without transition metals has been developed. The third chapter consists of the “Experimental Section”, which describes in detail all the experimental procedures for Chapter 2. This section includes all the synthetic and characterization data for all the compounds discussed in this thesis.

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