Della Pia, Ada, Riello, M., Stassen, D., Jones, T. S. (Tim S.), Bonifazi, D., De Vita, A. and Costantini, Giovanni (2016) Two-dimensional core–shell donor–acceptor assemblies at metal–organic interfaces promoted by surface-mediated charge transfer. Nanoscale, 8 (45). pp. 19004-19013. doi:10.1039/c6nr06527a ISSN 2040-3364.

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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:	Journal Article
Subjects:	Q Science > QC Physics Q Science > QD Chemistry
Divisions:	Faculty of Science, Engineering and Medicine > Science > Chemistry
Library of Congress Subject Headings (LCSH):	Electron donor-acceptor complexes, Charge transfer
Journal or Publication Title:	Nanoscale
Publisher:	Royal Society of Chemistry
ISSN:	2040-3364
Official Date:	2016
Dates:	Date Event 2016 Published 2 November 2016 Available 18 October 2016 Accepted 17 August 2016 Submitted
Volume:	8
Number:	45
Page Range:	pp. 19004-19013
DOI:	10.1039/c6nr06527a
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Open Access (Creative Commons)
Date of first compliant deposit:	28 February 2017
Date of first compliant Open Access:	28 February 2017
Funder:	Engineering and Physical Sciences Research Council (EPSRC), University of Warwick Postgraduate Research Scholarship, University of Warwick Institute of Advanced Study Scholarship, European Research Council (ERC), Royal Society (Great Britain), Belgium. Politique scientifique fédérale [Belgian State Science Policy Office] (BELSPO), Cardiff University, Fonds national de la recherche scientifique (Belgium) (FNRS), Birmingham Science City, Advantage West Midlands (AWM)
Grant number:	EP/G043647/1, EP/ G044864/1 (EPSRC), Grant “VISUAL-MS”, Grant “COLORLANDS” (ERC), Grant no. RG100917 (Royal Society), BELSPO-IAP 7/0 (BELSPO)

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