Evaluation of two- and three-coordinate copper(I) NHC complexes as photocatalysts

Abstract

This thesis explores the design, synthesis, optoelectronic properties, and photocatalytic testing of copper(I) complexes with a two- or three-coordinate geometry bearing N-heterocyclic carbene
ligands. Our design strategies aim to avoid the failings of four-coordinate copper(I) complexes which are prone to Jahn-Teller distortion in the excited state.

The first chapter provides an overview of the fundamental photophysical properties of transition metal complexes and an introduction to bimolecular energy and electron transfer processes. A
mini-review of Earth-abundant photocatalysts is presented. Special attention will then be devoted to describing the design principles of copper(I) based photocatalysts (PCs). We begin by describing the photophysical and electrochemical properties of four-coordinate copper(I) complexes, followed by the design and applications of copper(I) complexes as PCs. Next, we provide a summary of the development of two- and three-coordinate copper(I) complexes, describing their photophysical properties and applications.

Chapter 2 describes the synthesis, characterisation and optoelectronic properties of seven three-coordinate copper(I) N-heterocyclic carbene (NHC) complexes bearing N^N ligands, of the form of [Cu(IPr)(N^N)]PF₆ (where IPr is 1,3-Bis(2,6-diisopropylphenyl)imidazolium, and N^N is phen = 1,10-phenanthroline, bpy = 2,2’-bipyridine, dpa = 2,2’-dipyridylamine, mdpa = N-methyl-2,2’-dipyridylamine, dpym = di(pyridin-2-yl)methane, phdpym = 2,2'-(phenylmethylene)dipyridine, fludpym = 2,2'-(9H-fluorene-9,9-diyl)dipyridine). Six complexes underwent successful preliminary photocatalytic testing in two mechanistically distinct photocatalysis reactions: an Atom Transfer Radical Addition (ATRA) photoinduced electron transfer (PET) reaction between an alkyl halide and an alkene; and photoinduced energy transfer (PEnT) reaction of a vinyl azide to a vinyl nitrene, which subsequently rearranges to form a pyrrole. The complex [Cu(IPr)(phen)]PF₆ performed best in the ATRA reaction (77% NMR yield) out of six complexes tested, while complex [Cu(IPr)(phdpym)]PF₆ performed best in the PEnT reaction (59% NMR yield vs 66% obtained with [Cu(dmp)(BINAP)]BF₄).

Chapter 3 reports the synthesis, characterisation and optoelectronic properties of a series of three-coordinate copper(I) NHC complexes bearing a dpa ligand, of the form [Cu(NHC)(dpa)]PF₆.
Three complexes underwent preliminary photocatalytic testing, however their performance as PCs was poor.

Chapter 4 reports the first example of a neutral linear two-coordinate Cu(I) complex Cu(IPrBIAN)(Cz) bearing an IPrBIAN NHC ligand, and after investigation of its optoelectronic properties, it was successfully applied as a PC in a proof-of-concept PET ATRA reaction (52% NMR yield). Cu(IPrBIAN)(Cz) also exhibited interesting dual emission properties in solution; this is seen as separate emission depending on excitation source for most solvents, and is especially strong in chloroform solution. The synthesis, characterisation, and optoelectronic properties of further derivatives of this complex bearing 3,6-substituted carbazolate ligands were also investigated.

The final conclusions chapter summarises the results of each chapter and brings focus to the overarching aims and themes of the thesis. This chapter identifies key areas for future work in the field of two- and three-coordinate copper(I) complexes as photocatalysts, specifically the need to improve PC stability, investigate reaction mechanisms, and correlate structure-property relationships with photocatalytic performance. A need for standardisation of photocatalysis reaction set-ups is identified as a requirement for reproducibility of results within the field of photocatalysis.

Date of Award	14 Jun 2023
Original language	English
Awarding Institution	University of St Andrews
Supervisor	Eli Zysman-Colman (Supervisor)