This journal is c the Owner Societies 2012 Phys. Chem. Chem. Phys., 2012, 14, 1635–1641 1635 Cite this: Phys. Chem. Chem. Phys., 2012, 14, 1635–1641 Arylthio-substituted coronenes as tailored building blocks for molecular electronicsw Peter Kowalzik, a Nicolae Atodiresei,z b Marc Gingras,y c Vasile Caciuc, b Nicolas Schnaebele, d Jean-Manuel Raimundo, c Stefan Blu¨gel, b Rainer Waser a and Silvia Kartha¨userz* a Received 14th October 2011, Accepted 28th November 2011 DOI: 10.1039/c2cp23241c The electron transport through molecules in molecular devices is typically influenced by the nature of the interfaces with the contacting electrodes and by the interactions between neighbouring molecules. It is a major goal of molecular electronics to adjust the electronic function of a molecular device by tailoring the intrinsic molecular properties and the interfacial and intermolecular interactions. Here, we report on the tunability of the electronic properties of coronene derivatives, namely dodecakis(arylthio)coronenes (DATCs), which are found to exhibit a three-dimensional aromatic system. Scanning tunnelling microscopy (STM), spectroscopy (STS) and simulations based on the density functional theory (DFT) are employed to characterize the structural and electronic properties of these molecules deposited on Au(111) surfaces. It is shown that modifications of the peripheral aryl-groups allow us to specifically affect the self-assembly and the charge transport characteristics of the molecules. Molecular assemblies like supramolecular wires with highly delocalized orbitals and single molecules with molecular ‘‘quantum dot’’ characteristics are obtained in this way. 1. Introduction The development of future nanoelectronic devices based on single molecules or well-defined molecular assemblies is driven by the vision that a great variety of functionalities may be implemented by using the appropriate chemical design. 1,2 In the case of single molecule junctions, the charge injection and transport is naturally affected by the chemical structure of the molecule, but additionally the property of the electrode– molecule interface plays a significant or even dominant role. 3 The performance of organic electronic devices based on thin films or supramolecular architectures, on the other hand, crucially depends on the efficiency of the charge transport through the organic layer(s). 4,5 In this context, the existence of delocalized molecular orbitals throughout the whole molecule and sufficiently strong intermolecular interactions are the basis of conduction in organic semiconductors. In this study, we report on a molecular system based on a polycyclic aromatic hydrocarbon (PAH) core, more specifically coronene. A thorough phenylthio-substitution of coronene leads to dodecakis(phenylthio)coronene (DPTC), which is known to exhibit several unique (opto)electronic properties. 6 For instance, earlier spectroelectrochemical studies revealed a greater stabilization of the charged DPTC species, pointing to a larger delocalization of molecular orbitals, when compared to the non-substituted coronene. 7,8 These findings in combination with the non-planar molecular structure suggest that such molecules can be seen as nano- sized systems with a three-dimensional delocalized electronic network. Here, we focus on the self-assembly behaviour and the electronic properties of systematically varied dodecakis- (arylthio)coronenes (DATCs) derivatives, studied by STM/ STS measurements and theoretically investigated by first- principles calculations. It will be shown how the self-assembly of DATCs on Au(111) can be specifically directed into different regimes by using appropriate substituted arylthio moieties. A broad range of different electronic functionalities can be engineered along with the adsorption behaviour on the surface and the modification of the supramolecular structure. a Peter Gru ¨nberg Institut (PGI-7) and JARA-FIT, Forschungszentrum Ju ¨lich GmbH, 52425 Ju ¨lich, Germany. E-mail: s.karthaeuser@fz-juelich.de b Peter Gru ¨nberg Institut (PGI-1) and Institute for Advanced Simulation, Forschungszentrum Ju ¨lich GmbH, 52425 Ju ¨lich, Germany c CNRS, Aix-Marseille University, UPR 3118 CINAM, 13288 Marseille Cedex 09, France d University of Nice-Sophia Antipolis, 06108 Nice Cedex 2, France w Electronic supplementary information (ESI) available: Analytical data of the DATC derivatives. See DOI: 10.1039/c2cp23241c z Corresponding author for Ab initio calculations. y Corresponding author for organic synthesis and supramolecular chemistry. z Corresponding author for STM and electron transport studies. PCCP Dynamic Article Links www.rsc.org/pccp PAPER Downloaded by Forschungszentrum Julich Gmbh on 08/05/2013 13:11:15. Published on 28 November 2011 on http://pubs.rsc.org | doi:10.1039/C2CP23241C View Article Online / Journal Homepage / Table of Contents for this issue