Transition metal complexes of novel formazan ligands

Thorne, Madelaine 2026. Transition metal complexes of novel formazan ligands. PhD Thesis, Cardiff University. Item availability restricted.

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Abstract

The work presented in this thesis focuses on the development, synthesis and analysis of a series of formazan ligands, bearing a rarely reported tetradentate coordination environment, and their resultant group 10 metal complexes. Through strategic ligand design, the desirable optical and electrochemical behaviours offered insights into their structure-property relationships, including intense visible absorptions and scarcely reported luminescence. Chapter 2 investigates the synthesis of a diverse library of novel tetradentate ligands of both di-aryl and tri-aryl formazan structures. Tactical modulation of formazan substitution allowed for the development of both N4 and N2S2 coordination environments, both of which are unreported in the literature with respect to formazan chemistry. Additional substitution of electron-withdrawing and electron-donating groups on the periphery of the structure promoted fine-tuning of the electronic properties of the ligands and their resulting complexes. Chapter 3 draws direct comparisons between nine quinoline-functionalised formazanate complexes of Ni(II), Pd(II), and Pt(II) and reported analogous β-diketiminate systems. Such investigations allow for elucidation of formazans as electronically flexible alternatives to classical ligand systems. Chapter 4 describes the development of a series of Pt(II) formazanate complexes with thioether donor substituents. The hybridisation of classical formazanate electronic flexibility with softer dithizonate-type ligands proved well suited to coordination with third-row Pt(II) centres, resulting in five novel complexes with promising optical and electrochemical characteristics. ii Chapter 5 focuses on Pt(II) complexes of triaryl formazanate ligands, where the additional point of substitution allows for a higher degree of electronic tuning and the synthesis of asymmetric metal complexes. Chapter 6 extends the tetradentate formazanate chemistry beyond monometallic group 10 systems into heterobimetallic architectures. The successful isolation of an Re(I) complex bearing a neutral formazan ligand, and the subsequent coordination to Pt(II), demonstrates the ability of formazan ligands to support coordination at multiple metal centres.

Item Type:	Thesis (PhD)
Date Type:	Completion
Status:	Unpublished
Schools:	Schools > Chemistry
Date of First Compliant Deposit:	30 April 2026
Last Modified:	30 Apr 2026 14:01
URI:	https://orca.cardiff.ac.uk/id/eprint/186700

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