Article Title

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

Authors

Miao Yu, Interdisciplinary Nanoscience Center (iNANO) and Department of Physics and Astronomy, Aarhus University, Aarhus 8000, Denmark School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001, China
Wei Xu, Interdisciplinary Nanoscience Center (iNANO) and Department of Physics and Astronomy, Aarhus University, Aarhus 8000, Denmark
Nataliya Kalashnyk, Interdisciplinary Nanoscience Center (iNANO) and Department of Physics and Astronomy, Aarhus University, Aarhus 8000, Denmark
Youness Benjalal, Nanosciences group, CEMES-CNRS, Toulouse 31055, France Faculté des Sciences Ben M’Sik, Université Hassan II-Mohammédia, Casablanca BP 7955, Morocco
Samuthira Nagarajan, Nanosciences group, CEMES-CNRS, Toulouse 31055, France
Federico Masini, Interdisciplinary Nanoscience Center (iNANO) and Department of Physics and Astronomy, Aarhus University, Aarhus 8000, Denmark
Erik Lgsgaard, Interdisciplinary Nanoscience Center (iNANO) and Department of Physics and Astronomy, Aarhus University, Aarhus 8000, Denmark
Mohamed Hliwa, Nanosciences group, CEMES-CNRS, Toulouse 31055, France Faculté des Sciences Ben M’Sik, Université Hassan II-Mohammédia, Casablanca BP 7955, Morocco
Xavier Bouju, Nanosciences group, CEMES-CNRS, Toulouse 31055, France
André Gourdon, Nanosciences group, CEMES-CNRS, Toulouse 31055, France
Christian Joachim, Nanosciences group, CEMES-CNRS, Toulouse 31055, France
Flemming Besenbacher, Interdisciplinary Nanoscience Center (iNANO) and Department of Physics and Astronomy, Aarhus University, Aarhus 8000, Denmark
Trolle R. Linderoth, Interdisciplinary Nanoscience Center (iNANO) and Department of Physics and Astronomy, Aarhus University, Aarhus 8000, Denmark

Keywords

perylene-3, 4, 9, 10-tetracarboxylic diimide (PTCDI), molecular self-assembly, hydrogen bonding, electrostatic interaction, scanning tunneling microscopy

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.

Graphical Abstract

DOI

https://doi.org/10.1007/s12274-012-0274-6

Publisher

Tsinghua University Press

Recommended Citation

Miao Yu,Wei Xu,Nataliya Kalashnyk,Youness Benjalal,Samuthira Nagarajan,Federico Masini,Erik Lægsgaard,Mohamed Hliwa,Xavier Bouju,André Gourdon,Christian Joachim,Flemming Besenbacher,Trolle R. Linderoth, 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. NanoRes.2012, 5(12): 903–916