Communications
DOI: 10.1002/anie.201008212
Self-Assembly
Janus-Like 3D Tectons: Self-Assembled 2D Arrays of Functional Units
at a Defined Distance from the Substrate**
David Blꢀger, Fabrice Mathevet, David Kreher, Andrꢀ-Jean Attias,* Amandine Bocheux,
Sylvain Latil, Ludovic Douillard, Cꢀline Fiorini-Debuisschert, and Fabrice Charra*
Supramolecular-based architectures onto surfaces have been
widely investigated during the past two decades.[1] The most
commonly employed strategies to create 2D hierarchical
structures exploit noncovalent molecular interactions
between planar tectons. Various approaches have been
explored to generate highly ordered monocomponent struc-
tures and multicomponent assemblies.[2] In addition to the
control of molecule positioning that leads to complex nano-
patterns, the control of surface properties has also been
addressed more recently. In that respect, nanoporous net-
works are of particular interest. Owing to the host properties
of these networks towards organic guests, they allow for
addressing various interesting aspects such as molecular
dynamics, selection, recognition, and immobilization, hence
leading to functional surfaces.[3]
Besides these features confined in-plane, the demanding
forthcoming applications in nanotechnology require to create
out-of-plane functions and to be able to fully exploit the space
above the substrate. Accessing the third dimension is
mandatory for the progress of for example, molecular
electronics and photonics, in which the proximity of adsorbed
photoactive units with conducting substrates results in a fast
quenching of electronic excitations.[4] To avoid this drawback,
the decoupling between active molecular units and conduct-
ing substrates is currently achieved by lifting the molecule,
either by covering the surface with a uniform insulating
layer[5] or through the attachment of bulky chemical side
groups (e.g. tert-butyl groups) to the molecule, which act as
spacer legs that lead to the so-called molecular “landers”.[6]
However, these examples suffer from limited short-range in-
plane organizations. Several ways are explored to circumvent
this problem based on molecular self-assembly. They consist
in controlling interactions between 3D tectons, for example
with H-bonded molecular “landers”,[7] or in exploiting a self-
assembled insulating layer as template for an upper functional
layer.[8] In this context, the development of general and
versatile methods for the design of 3D tectons that are able to
self-assemble with long-range lateral order and to expose the
desired functionality at a defined distance from the surface,
remains an open challenge.
In a previous work[9] we demonstrated the 2D self-
assembly of building blocks with intermolecular noncovalent
bonding units (the so-called “clips”) on highly-oriented
pyrolytic graphite (HOPG) at the liquid–solid interface.
More precisely, we showed that the attachment of clips to
the lower-deck of multilayered [2.2]paracyclophane deriva-
tives leads to the self-assembly of building blocks that are
oriented face-on with the cyclophane rings that stack
perpendicularly to the substrate.[10]
Herein, we introduce the concept of Janus-like 3D
molecular tectons, which are doubly-functionalized building
blocks that expose two opposite faces (A and B) linked by a
rigid spacer. A is a pedestal designed for guiding 2D self-
assembly on the substrate (HOPG) and B is a functional
moiety. We show that the in-plane self-assembling ability of A
controls the positioning of the out-of-plane moiety B.
As a first example to illustrate this concept, we designed
and synthesized the 3D tecton 1 (Figure 1), which was
obtained as a racemic mixture (1,1’) because of the planar
chirality inherent to asymmetrically functionalized paracy-
clophanes.[11] The target compounds (1,1’) combine 1) a
pedestal that consists of two molecular clips able to self-
assemble on HOPG, 2) a [3.3]dithiaparacyclophane unit[12]
3.3 ꢀ in height that acts as a two-story linker, and 3) a
functional molecule, namely a distyrylbenzene fluorophore
(highlighted in blue in Figure 1). This building block is
designed to act as a Janus tecton, that is, it self-assembles in a
well-organized in-plane monolayer and distributes the func-
tional units according to a periodic pattern that parallels its
subjacent counterpart several ꢀ higher, thanks to the para-
cyclophane pillar. To confirm this behavior, STM experiments
were carried out in situ, that is, at the solid–liquid interface.
As a guide to the interpretation of STM images, DFT
modeling has been performed on this system.
[*] Dr. D. Blꢀger, Dr. F. Mathevet, Dr. D. Kreher, Prof. A.-J. Attias,
A. Bocheux
Laboratoire de Chimie des Polymꢁres-UMR 7610
Universitꢀ Pierre et Marie Curie
4 place Jussieu—case 185, 75252, Paris Cedex 05 (France)
E-mail: andre-jean.attias@upmc.fr
Dr. D. Blꢀger
Current address: Laboratory of Organic Chemistry and Functional
Materials, Department of Chemistry
Humboldt Universitꢂt zu Berlin
Brook-Taylor-Strasse 2, 12489 Berlin (Germany)
A. Bocheux, Dr. S. Latil, Dr. L. Douillard, Dr. C. Fiorini-Debuisschert,
Dr. F. Charra
Laboratory for Organic Electronics and Nanophotonics
Service de Physique et Chimie des Surfaces et Interfaces, IRAMIS
CEA 91191 Cedex (France)
E-mail: fabrice.charra@cea.fr
[**] We thank the Agence Nationale de la Recherche (ANR) for generous
support through the NOMAD project. D.B. acknowledges the
Ministꢁre de la Recherche et de l’Ensignement Supꢀrieur (MESR)
for providing a doctoral fellowship.
The overall synthetic route to the Janus-like building
block (1,1’) is outlined in Scheme 1 (see the Supporting
Supporting information for this article is available on the WWW
6562
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2011, 50, 6562 –6566