Study of Supramolecular Interactions and Their Exploration in Catalysis

Kumari, Nidhi (2026) Study of Supramolecular Interactions and Their Exploration in Catalysis. PhD thesis, Indian Institute of Science Education and Research Kolkata.

Text (PhD thesis of Nidhi Kumari (20RS002)) 20RS002.pdf - Submitted Version Restricted to Repository staff only Download (14MB)

Abstract

This thesis is structured to address two distinct facets of supramolecular chemistry, i.e., fundamentals of supramolecular chemistry – structure and connectivity, and applications of supramolecular chemistry in catalysis. We have spent some time on a comprehensive overview of supramolecular chemistry, which is vital for designing an innovative material as it comprises non-covalent interactions that assemble the individual molecules into a complex functional structure, thereby introducing the principles of supramolecular chemistry by leveraging soft-oxometalates (SOMs)-based systems that our group has explored to craft a pillar for a sustainable future. Thereafter, the problem statement has been defined in this thesis work. Fundamental insights into supramolecular interactions are covered in Chapters 3, 4, and 5, where we discuss the variation in hydrogen bond interactions through liquid-liquid phase transitions, which create a 2D glassy crystal at the interface. Further, phase transitions of paracetamol have been explored through the ternary phase diagram, which demonstrates that the nucleation process depends on the dielectric constant or solvent ratio, and the crystal phase emerges from the colloidal phase, which is a metastable state. On varying the solvent system, we have obtained both monoclinic and orthorhombic polymorphic forms. Further, we demonstrate the visible light-driven conversion of SOMs, Mo₁₃₂ to Mo₁₅₄, mediated via water splitting. After gaining insight into supramolecular interactions that promote the effective trapping of different phases, designing novel metal materials, and the formation of polymorphic forms, we will move to the application part, where different catalyst systems are engineered for the activation of the C-H bond and CO₂. In Chapter 6, we will demonstrate the conversion of benzene to phenol via C-H activation at ambient conditions using a soft-oxometalate-based catalyst, (NH₄)₆6V₁₀O₂₈ · 6H₂O, and Eosin Y as the photosensitizer. Thereafter, in chapters 7, 8, and 9, we addressed a groundbreaking pathway for the direct conversion of carbon dioxide into C₁, C₂, and C₃ products through metal-free pre-catalysts that comprise Azo and dithiol moieties, and contribute to the development of renewable and sustainable value-added commodities.

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