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Two-dimensional core-shell donor-acceptor assemblies at metal-organic interfaces promoted by surface-mediated charge transfer

Della Pia, A, Riello, M, Stassen, D, Jones, T.S., Bonifazi, Davide, De Vita, A and Costantini, G 2016. Two-dimensional core-shell donor-acceptor assemblies at metal-organic interfaces promoted by surface-mediated charge transfer. Nanoscale 8 , pp. 19004-19013. 10.1039/C6NR06527A

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Abstract

Organic charge transfer (CT) complexes obtained by combining molecular electron donors and acceptors have attracted much interest due to their potential applications in organic opto-electronic devices. In order to work, these systems must have an electronic matching – the highest occupied molecular orbital (HOMO) of the donor must couple with the lowest unoccupied molecular orbital (LUMO) of the acceptor – and a structural matching, so as to allow direct intermolecular CT. Here it is shown that, when molecules are adsorbed on a metal surface, novel molecular organizations driven by surface-mediated CT can appear that have no counterpart in condensed phase non-covalent assemblies of donor and acceptor molecules. By means of scanning tunneling microscopy and spectroscopy it is demonstrated that the electronic and self-assembly properties of an electron acceptor molecule can change dramatically in the presence of an additional molecular species with marked electron donor character, leading to the formation of unprecedented core-shell assemblies. DFT and classical force-field simulations reveal that this is a consequence of charge transfer from the donor to the acceptor molecules mediated by the metallic substrate.

Item Type: Article
Date Type: Published Online
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: Royal Society of Chemistry
ISSN: 2040-3372
Date of First Compliant Deposit: 10 January 2017
Date of Acceptance: 18 October 2016
Last Modified: 27 Oct 2018 06:42
URI: http://orca.cf.ac.uk/id/eprint/97307

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