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Surface deposition of peripherally-functionalised Oligo-Porphyrazines using Ring Opening Metathesis Polymerisation


Interest in the miniaturisation and fabrication of nanoscale electronic devices has blossomed in recent years. A significant goal in this field is to prepare lines/patterns that are conducting (i.e., wires), and whose conductivity can be modulated (i.e., devices) as such patterns are of interest in optical, electrical, and sensing devices. The proposed interdisciplinary research project entails the synthesis and the study of the properties and applications of new materials - electroactive porphyrazines (pzs ) and porphyrazine (pz) oligomers, bound and spatially addressed on gold surfaces, which may be used for the development of nanoscale wires and devices. Recently, in a collaborative effort, the Barrett group (Imperial College, UK), along with Hoffman and Mirkin groups (Northwestern University, USA) have shown that pz orientation in a self-assembled mono-layer has a remarkable influence on its electrochemical properties.

This publication is the first report that examines the influence of molecular proximity/orientation to a metallic surface in controlling the reduction potentials of a surface nanostructure. Generation of oligo-pzs with variation in molecular weight and tertiary structure should be important in further understanding the pz-gold interactions. We propose to prepare a range of novel pz derivatives with pendent benzobicyclo[2.2.2]octadiene residues. These will be attached to gold surfaces through pendent thiol residues, using dip-pen nanolithography.

These primer macrocycles will be used to initiate and anchor porphyrazine oligomers to the surface using ring opening metathesis polymerisation. The gold surface appended oligo-pzs and derived oxidation products will be characterised by electrochemical measurements and atomic force microscopy. The results of this project should be of direct and immediate relevance to both academic and industrial scientists concerned with optical materials, high performance electro-active polymers, and device fabrication.

Field of science

  • /natural sciences/chemical sciences/inorganic chemistry/inorganic compounds

Call for proposal

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Funding Scheme

IIF - Marie Curie actions-Incoming International Fellowships