Design and Development of Fe and Ni Metallaphotoredox Methods Restricted; Files & ToC
Nsouli, Reem (Fall 2025)
Abstract
Photoredox catalysis has emerged as a powerful strategy in modern organic synthesis. In particular, metallaphotoredox has proven to be a modular platform for C–C and C–X bond formation under mild conditions by leveraging the synergy between photocatalysts and transition metal catalysts. Traditionally, Ir- and Ru-based complexes have dominated this field due to their long-lived excited states and well-defined photophysical properties. However, growing concerns regarding cost, toxicity, and sustainability have motivated the search for more earth-abundant alternatives. Fe presents a unique candidate as it is the second most abundant metal in the earth’s crust and is therefore inexpensive and benign. Additionally, Fe-based photoredox systems can undergo an orthogonal inner-sphere electron transfer mechanism, in which pre-coordination of the substrate in-situ precedes excitation-induced bond homolysis. This unique pathway provides the opportunity for chemoselective activation of substrates independent of redox potentials. Despite these advantages, the adoption of Fe in metallaphotoredox is still underdeveloped.
This dissertation first describes the use of Fe photoredox in a synergistic decarboxylative arylation strategy with Ni, providing a mechanistic framework complementary to precedented Ir and Ni methods. Additionally, the importance of ligands to expand substrate compatibility for efficient Fe-mediated decarboxylation is highlighted. The second part of this dissertation develops technology that affords exploration of new photoredox catalysts that can lead to sustainable chemistry advances. We introduce a custom-designed 24-well photoreactor that allows independent control of wavelength, intensity, and irradiation on a per-well basis. This programmable platform transforms light from being a fixed experimental parameter in high-throughput screening into a tunable variable, enabling broad exploration of photocatalytic reactivity across a wide range of conditions. Benchmarking studies demonstrated comparable performance to state-of-the-art photoredox plates with excellent reproducibility across the different wells. The unique utility and features of this platform were further showcased by examining photocatalytic reactions that require different wavelengths and duration of irradiation within the same experiment. Together, these advances establish one of the first examples of an inner-sphere Fe photoredox catalyst paired with a Ni cross-coupling catalyst and provide a customized platform for accelerating discovery of photocatalytic transformations.
Table of Contents
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About this Dissertation
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File download under embargo until 12 January 2032 | 2025-12-15 23:29:28 -0500 | File download under embargo until 12 January 2032 |
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