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Research Article

From Zero to Two Dimensions: Supramolecular Nanostructures Formed from Perylene-3,4,9,10-tetracarboxylic Diimide (PTCDI) and Ni on the Au(111) Surface Through the Interplay Between Hydrogen-Bonding and Electrostatic Metal–Organic Interactions

Miao Yu1,4, Wei Xu1, Nataliya Kalashnyk1, Youness Benjalal2,3, Samuthira Nagarajan2, Federico Masini1, Erik Lægsgaard1, Mohamed Hliwa2,3, Xavier Bouju2, André Gourdon2, Christian Joachim2, Flemming Besenbacher1( ), Trolle R. Linderoth1( )
Interdisciplinary Nanoscience Center (iNANO) and Department of Physics and AstronomyAarhus UniversityAarhus8000Denmark
Nanosciences groupCEMES-CNRSToulouse31055France
Faculté des Sciences Ben M'sikUniversité Hassan II-MohammédiaCasablanca, BP 7955Morocco
School of Chemical Engineering and TechnologyHarbin Institute of TechnologyHarbin150001China
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Abstract

Supramolecular self-assembly of the organic semiconductor perylene-3, 4, 9, 10-tetracarboxylic diimide (PTCDI) together with Ni atoms on the inert Au(111) surface has been investigated using high-resolution scanning tunneling microscopy under ultrahigh vacuum conditions. We demonstrate that it is possible by tuning the co-adsorption conditions to synthesize three distinct self-assembled Ni-PTCDI nanostructures from zero-dimensional (0-D) nanodots over one-dimensional (1-D) chains to a two-dimensional (2-D) porous network. The subtle interplay among non-covalent interactions responsible for the formation of the observed structures has been revealed from force-field structural modeling and calculations of partial charges, bond orders and binding energies in the structures. A unifying motif for the 1-D chains and the 2-D network is found to be double N-H…O hydrogen bonds between PTCDI molecules, similar to the situation found in surface structures formed from pure PTCDI. Most interestingly, we find that the role of the Ni atoms in forming the observed structures is not to participate in metal-organic coordination bonding. Rather, the Ni adatoms acquire a negative partial charge through interaction with the substrate and the Ni-PTCDI interaction is entirely electrostatic.

Keywords

perylene-3, 4, 9, 10-tetracarboxylic diimide (PTCDI)molecular self-assemblyhydrogen bondingelectrostatic interactionscanning tunneling microscopy

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Nano Research
Volume 5 Issue 12,
December 2012
Pages 903-916
DOI: 10.1007/s12274-012-0274-6
Cite this article:
Yu M, Xu W, Kalashnyk N, et al. From Zero to Two Dimensions: Supramolecular Nanostructures Formed from Perylene-3,4,9,10-tetracarboxylic Diimide (PTCDI) and Ni on the Au(111) Surface Through the Interplay Between Hydrogen-Bonding and Electrostatic Metal–Organic Interactions. Nano Research, 2012, 5(12): 903-916. https://doi.org/10.1007/s12274-012-0274-6

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Received: 03 August 2012
Revised: 11 October 2012
Accepted: 25 October 2012
Published: 15 November 2012
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2012
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