Multidecker assemblies from Porphyrin and Phthalocyanine derivatives

Alsaiari, Norah (2022) Multidecker assemblies from Porphyrin and Phthalocyanine derivatives. Doctoral thesis, University of East Anglia.

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Abstract

The work set out in this thesis focuses on the synthesis and investigations of linked heteroleptic triple deckers (TD) based on porphyrin-phthalocyanine-porphyrin analogues. They are interesting materials because of the potential applications of lanthanide-bridged triple and double deckers in molecular devices. Research on their synthesis has taken huge steps forward in recent years. They also have low oxidation potentials, as well as reversible electrochemistry. Such remarkable features give these complexes great potential for their use in several applications, for example, molecular magnets, multibit molecular information storage, sensors, nonlinear optical materials, nanomaterials and field effect transistors that cannot be achieved by their mono- metallic macrocycle counterparts. A number of multidecker systems have previously been synthesised by Cammidge group.

Firstly, this current research focuses on phthalocyanine and related macrocycles by attempting to synthesise unsymmetrical systems that could be inserted in a triple-decker formed by the reaction with linked porphyrins, with a view to preparing higher order structures through linking this unsymmetrical central macrocycle. However, insertion of the selected phthalocyanines proved challenging. Triple decker structures were formed and isolated, but characterisation proved challenging, and the spectroscopic results could not prove that simple porphyrin-phthalocyanine-porphyrin were formed.

Secondly, we switched to the synthesis of alternative macrocycles such as tetrabenzotriazaporphyrins (TBTAPs) which are hybrid structures that lie between the parent phthalocyanine and tetrabenzoporphyrin macrocylces. Importantly, the meso carbon opens up a variety of possibilities in the TBTAPs. The synthesis of triple deckers with different meso- substituted TBTAPs has been achieved but the spectroscopic characterisation was much more complicated as compared to the previous symmetric phthalocyanine derivatives. Rotation is hindered (NMR) in these cases. Finally, the decision was taken to investigate a different class of multichromophore assemblies. We aimed to synthesise a compound that bears a more rigid element to the bridge that could be further functionalised or dimerised. Triple deckers of compounds that bear a more rigid element (such as benzene and porphyrin) to the bridge were successfully synthesised using the developed procedure for the selective formation of linked closed triple deckers, and overall, this appears to be a very promising strategy for building up more complex arrays of TDs.

Item Type:	Thesis (Doctoral)
Faculty \ School:	Faculty of Science > School of Chemistry
Depositing User:	Chris White
Date Deposited:	21 Jun 2023 13:25
Last Modified:	21 Jun 2023 13:25
URI:	https://ueaeprints.uea.ac.uk/id/eprint/92458
DOI:

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