Multi-decker assemblies from porphyrin derivatives

Al-Yami, Reem Ali (2025) Multi-decker assemblies from porphyrin derivatives. Doctoral thesis, University of East Anglia.

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Abstract

There has been a huge development in the study of sandwich-type complexes over the past few decades. The work set out in this thesis focuses on the synthesis and investigations of linked heteroleptic triple-deckers (TDs) based on porphyrin-porphyrin-porphyrin. They are interesting materials because of the potential applications of the lanthanide-bridged triple deckers in single-molecule magnets (SMM) and in thin-film transistors (OTFT). This thesis describes various methods for the synthesis of lanthanide mixed-porphyrin triple-decker complexes. These triple-deckers are formed from a symmetrical dyad containing two porphyrin molecules linked together by a flexible decyl or dodecyl chain. The optimisation of the synthesis of these dyads, and the precursor monohydroxyphenyl porphyrin (TPPOH), took significant time and the improvements are discussed in detail. Triple-decker synthesis focused mostly on the use of commercially available octaethylporphyrin (OEP). Unlike the smooth synthesis of related triple deckers employing phthalocyanine as the third ring, reported by our group and found to exclusively produce the symmetrical TD with the phthalocyanine in the middle, syntheses using OEP were more challenging. Conditions for the synthesis were eventually achieved, and they are discussed. Most interestingly, the isolated TD has a different structure to that previously observed with phthalocyanine, in that OEP is found to occupy an external site in the sandwich (BAA structure). Complexes with La, Nd, and Pr were successfully prepared and characterised, and crystals suitable for XRD analysis were obtained to prove the assignment of the BAA arrangement. Other porphyrins (octamethyl porphyrin, tetraphenyl porphyrin, protoporphyrin) were briefly examined and gave mixed results. While inconclusive, the results demonstrate scope for further development of this triple-decker chemistry to deliver a range of heteroleptic complexes where the order of assembly is controlled by (presumably) steric factors.

Item Type:	Thesis (Doctoral)
Faculty \ School:	Faculty of Science > School of Chemistry, Pharmacy and Pharmacology
Depositing User:	Chris White
Date Deposited:	20 Jan 2026 13:41
Last Modified:	20 Jan 2026 13:41
URI:	https://ueaeprints.uea.ac.uk/id/eprint/101658
DOI:

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