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Main group elements have recently emerged as benign and cost-effective alternatives to transition metals in organometallic chemistry. By finely tuning their electronic structure, these elements can engage in substrate coordination, activate small molecules, and even catalyse redox reactions, mirroring the behaviour of transition metals. This book chapter aims to summarize a relatively underexplored area within main group metal chemistry: their ability to undergo photoinduced processes such as redox reactivity, rearrangements, and radical formation.

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