Controlled synthesis of lanthanide triple-decker complexes comprising up to three different porphyrinoids

Soobrattee, Shazia Camilla (2024) Controlled synthesis of lanthanide triple-decker complexes comprising up to three different porphyrinoids. Doctoral thesis, University of East Anglia.

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Abstract

Sandwich double and triple decker complexes of phthalocyanine, porphyrins or a mixture of both exhibit particular π-π interactions responsible for their special physical, spectroscopic and electrochemical properties. These properties make them especially suitable for applications such as such as field effect transistors, nonlinear optical materials, sensors, molecular magnets, and multibit molecular information storage, unlike the mono-metallic macrocycle counterparts.

This thesis describes various methods for the synthesis of porphyrin-phthalocyanine-tetrabenzotriazaporphyrin triple decker complexes. These triple deckers contain either an unsymmetrical or a symmetrical dyad. The unsymmetrical dyad contains a porphyrin and a tetrabenzotriazaporphyrin molecules linked together by a flexible decyl and dodecyl chain while the symmetrical dyad consists of two tetrabenzotriazaporphrin molecules linked together by a decyl chain. Phthalocyanine and different lanthanide metals such as La, Nd, Eu, were incorporated into the sandwich structure. The synthetic challenges are discussed, and the eventual successful methods described, the ‘one pot’ reaction was found to be the most efficient. Spectroscopic analysis such as MALDI-TOF MS, NMR and UV-Vis were used to identify and determine the structure of the synthesised triple deckers. When La salt was used in the synthesis, the results obtained from both unsymmetrical C10 and C12 dyad were similar but differ from the known the porphyrin-phthalocyanine-porphyrin triple decker. It is found that the phthalocyanine unit is not in the middle of the sandwich and lies on the outside next to the Por unit rather than the tetrabenzotriazaporphrin unit. X-Ray crystallography analysis would give a conclusive result, however so far suitable crystals were not grown successfully. Many attempts to synthesise the La triple decker using the symmetrical dyad and phthalocyanine proved to be unsuccessful, instead, a double decker was formed. An unexpected result was obtained from the Nd triple decker synthesis where one of the fractions has its units orientated as follows porphyrin-phthalocyanine-tetrabenzotriazaporphrin, while the UV-Vis of the other fraction was similar to the newly synthesised La triple decker. The Eu triple decker has its units oriented similar to one of the fractions of Nd triple decker that is exclusively porphyrin-phthalocyanine-tetrabenzotriazaporphrin.

Item Type:	Thesis (Doctoral)
Faculty \ School:	Faculty of Science > School of Chemistry (former - to 2024)
Depositing User:	Chris White
Date Deposited:	15 Oct 2024 07:40
Last Modified:	15 Oct 2024 07:40
URI:	https://ueaeprints.uea.ac.uk/id/eprint/97023
DOI:

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