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Nanoscale Aromaticity and Supramolecular Electronic Materials

Project description

Study sheds more light on the unusual properties of large aromatic rings

Molecules such as benzene are known as aromatic compounds. If a magnetic field is directed perpendicular to the plane of an aromatic system, a ring current is induced in the delocalised pi electrons of the aromatic ring. Aromaticity was long thought to be restricted to small molecules, but recent research has shown that circuits of more than 160 pi electrons can exhibit strong aromatic ring currents. The EU-funded ARO-MAT project will explore the effects of molecular size and topology on aromaticity. The study will focus on the electronic and magnetic phenomena in molecules with dimensions of 5–25 nm (as big as many proteins). Fundamental knowledge generated during the project could serve as a basis for developing materials with unprecedented electronic and magnetic properties.

Objective

ARO-MAT will target emergent cooperative electronic and magnetic phenomena in molecules with dimensions of 5–25 nm (i.e. as big as many proteins). The project will develop supramolecular architectures with large pi-systems and well-defined geometries, in which the frontier orbitals coherently delocalize charge over the whole nanostructure. Aromaticity is a key emergent phenomenon; it can be defined as the ability of a cyclic molecule to sustain a ring current when placed in a magnetic field. Until recently, it was thought that aromaticity is restricted to small molecules, with circuits of less than about 22 pi-electrons. Anderson has shown that circuits of more than 160 pi-electrons (circumference > 15 nm) can exhibit strong aromatic ring currents. Testing even larger rings will elucidate the link between aromaticity and the persistent currents found in non-molecular mesoscopic rings (diameter 50–500 nm). ARO-MAT will explore the effects of molecular size and topology on nanoscale aromaticity. Other emergent phenomena to be addressed include the formation of open-shell singlet polyradical ground states, magnetic bistability in systems with many paramagnetic metal centers, and the control of charge transport through single-molecule devices by quantum interference. This multidisciplinary project combines organic synthesis, supramolecular chemistry, theory, electronic structure calculations, NMR and EPR spectroscopy, magnetochemistry, molecular electronics and low-temperature charge transport experiments. The core objective is to create low band gap materials with unprecedented electronic and magnetic properties, and to understand the structure-property relationships governing the behavior of these new materials. Most of the target structures are based on metalloporphyrins because of their redox activity, stability, structural versatility, suitability for template-directed synthesis and ability to position multiple strongly coupled paramagnetic metal centers.

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Programme(s)

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Topic(s)

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Funding Scheme

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ERC-ADG - Advanced Grant

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Call for proposal

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(opens in new window) ERC-2019-ADG

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Host institution

THE CHANCELLOR, MASTERS AND SCHOLARS OF THE UNIVERSITY OF OXFORD
Net EU contribution

Net EU financial contribution. The sum of money that the participant receives, deducted by the EU contribution to its linked third party. It considers the distribution of the EU financial contribution between direct beneficiaries of the project and other types of participants, like third-party participants.

€ 2 491 625,00
Address
WELLINGTON SQUARE UNIVERSITY OFFICES
OX1 2JD Oxford
United Kingdom

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Region
South East (England) Berkshire, Buckinghamshire and Oxfordshire Oxfordshire
Activity type
Higher or Secondary Education Establishments
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Total cost

The total costs incurred by this organisation to participate in the project, including direct and indirect costs. This amount is a subset of the overall project budget.

€ 2 491 625,00

Beneficiaries (1)

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