One‐Dimensional Assembly and Selective Orientation of Lander Molecules on an O–Cu Template

Otero, Roberto; Naitoh, Yoshitaka; Rosei, Federico; Jiang, Ping; Thostrup, Peter; Gourdon, André; Lægsgaard, Erik; Stensgaard, I.; Joachim, Christian; Besenbacher, Flemming

doi:10.1002/anie.200353586

Cited by 106 publications

(80 citation statements)

References 24 publications

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“…In order to test the quality of the geometrical results for the molecular structures we have carried out a series of calculations using different methods: the semiempirical hamiltonian AM1 available in the GAMESS package [27], and the ab initio density functional methods Siesta [28,29] and state-of-the-art DMOL3 [30,31] in the local density approximation. The obtained structural dimensions are very consistent and in very good agreement with the estimated experimental data from STM experiments [15,19,33,34], indicating that the used molecular force field reproduces the VL geometrical features quite well.…”

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confidence: 81%

Lock-and-key effect in the surface diffusion of large organic molecules probed by STM

et al. 2004

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Violet Lander (VL) (C108H104) is a large organic molecule that when deposited on Cu (110) exhibited lock-and-key like behavior (Otero et al., Nature Mater. 3, 779 (2004)). In this work we report on a detailed fully atomistic molecular dynamics study of this phenomenon. Our results show that it has its physical basis in the interplay of the molecular hydrogens and the Cu(110) atomic spacing, which is a direct consequence of an accidental commensurability between molecule and surface dimensions. This knowledge could be used to engineer new molecules capable of displaying lock-and-key behavior with new potential applications in nanotechology.PACS numbers: 61.46.+w, 68.37.Lp, With the advent of nanoscience and nanotechnology and the perspective of molecular electronics [1,2,3,4,5,6,7], significant theoretical and experimental efforts have been devoted to the study of the complex interactions involving organic molecular structures and metallic surfaces [8,9,10,11,12,13,14,15]. One essential aspect of these phenomena is to understand how these interactions alter the properties of both molecule and surface. Recent progress has been achieved through the use of UHV-STM (ultrahigh vacuum-scanning transmission microscopy) [10,16] that allowed the identification of important structural and dynamical features related to the behavior of molecular wires adsorved on metallic surfaces.One important family of molecular wires is the socalled "Lander molecules" (because of its resemblance to a Mars surface rover) [17]. These large organic molecules are composed of a rigid polyaromatic π central board and four spacers (legs) of up to eight 3,5-di-tert-butylphenyl σ-bonded to the central board (Fig. 1). These spacers generate a configuration where the phenyl groups are nearly perpendicular to the main board plane by steric crowding. When deposited onto a metallic surface, these conformations allow an electronic decoupling (π-bonded from the metallic surface) to occur. Also, the presence of the tert-butyl groups, which increases the board-surface distance, permits some rotation of the "legs" without significantly reducing this distance. When adsorbed on Cu(100) or Cu(110) surfaces, the Lander molecule can act as a template for selfaccomodating metal atoms at the step edges of the copper substrate, spontaneously generating metallic nanostructures dimensionally commensurable with the Lander

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Lock-and-key effect in the surface diffusion of large organic molecules probed by STM

et al. 2004

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“…The off-specular diffraction appearing as symmetrically placed satellite peaks aside the specular peak is a complementary demonstration of the periodicity of the supramolecular arrangement. Finally, HAS substantiates the room temperature stability of the gratings, which is an important feature for their potential application as templates structures (35). XPS measurements clarify the chemical state of the amino acid moiety.…”

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Zwitterionic self-assembly of l -methionine nanogratings on the Ag(111) surface

Schiffrin

Riemann

Auwärter

et al. 2007

Proc. Natl. Acad. Sci. U.S.A.

165

236

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The engineering of complex architectures from functional molecules on surfaces provides new pathways to control matter at the nanoscale. In this article, we present a combined study addressing the self-assembly of the amino acid L-methionine on Ag(111). Scanning tunneling microscopy data reveal spontaneous ordering in extended molecular chains oriented along high-symmetry substrate directions. At intermediate coverages, regular biomolecular gratings evolve whose periodicity can be tuned at the nanometer scale by varying the methionine surface concentration. Their characteristics and stability were confirmed by helium atomic scattering. X-ray photoemission spectroscopy and high-resolution scanning tunneling microscopy data reveal that the L-methionine chaining is mediated by zwitterionic coupling, accounting for both lateral links and molecular dimerization. This methionine molecular recognition scheme is reminiscent of sheet structures in amino acid crystals and was corroborated by molecular mechanics calculations. Our findings suggest that zwitterionic assembly of amino acids represents a general construction motif to achieve biomolecular nanoarchitectures on surfaces.nanochemistry ͉ scanning tunneling microscopy ͉ supramolecular engineering ͉ surface chemistry ͉ x-ray photoemission spectroscopy T he controlled self-assembly of functional molecular species on well defined surfaces is a promising approach toward the design of nanoscale architectures (1). By using this methodology, regular low-dimensional systems such as supramolecular clusters, chains, or nanoporous arrays can be fabricated (2-6). A wide variety of molecular species as well as substrate materials proved to be useful (7), exploiting noncovalent directional interactions including dipole-dipole coupling (2, 3), hydrogen bridges (4,5,(8)(9)(10)(11), and metal-ligand interactions (6,(12)(13)(14)(15). With the exception of multiple H-bonded networks or coordination networks incorporating metal centers, it remains challenging to realize robust systems, and there is a need to develop protocols exploiting stronger intermolecular bonds to realize purely organic low-dimensional architectures. Small biological molecules such as amino acids or DNA base molecules represent an important class of building blocks that are of interest for molecular architectonic on surfaces because they inherently qualify for molecular recognition and self-assembly (16)(17)(18)(19)(20). The interaction between biomolecules and solid surfaces is decisive for the development of bioanalytical devices or biocompatible materials (21-23) as well as for a fundamental understanding of protein-surface bonding (24). Moreover, in three dimensions the amino acids provide assets to engineer distinct network structures based on zwitterionic coupling schemes (25-27), which may be categorized as subclass of ionic self-assembly (28), and thus are promising units to create robust nanoarchitectures. However, to date, the advantages of zwitterionic supramolecular synthons have not been exploited in ...

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“…50). The width of the stripes can be adjusted by varying the oxygen pressure and the substrate temperature during the oxidation process [130]. The O-Cu nanotemplate can be used to drive highly ordered patterns of organic molecules based on their higher affinity for the clean Cu areas rather than the oxygen passivated stripes.…”

Section: Long-range Mesoscale Reconstructionsmentioning

confidence: 99%

“…Moreover, adsorption geometries and self-assembled patterns of organic molecules can be simultaneously studied on two different surfaces, namely, the metallic and the oxygen-passivated Cu (110). The template has been employed to pattern onedimensional and two-dimensional nanostructures of organic molecules, including fullerenes [131], the so-called Lander molecules [130][131][132][133][134] and the organic semiconductors α-quinquethiophene (T5) [135] and rubrene [136]. The same system has been used to study the electronic properties and the Reprinted with permission from [132].…”

Section: Long-range Mesoscale Reconstructionsmentioning

confidence: 99%

Two-Dimensional Nanotemplates as Surface Cues for the Controlled Assembly of Organic Molecules

Cicoira

Santato

Rosei

2008

Topics in Current Chemistry

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One‐Dimensional Assembly and Selective Orientation of Lander Molecules on an O–Cu Template

Cited by 106 publications

References 24 publications

Lock-and-key effect in the surface diffusion of large organic molecules probed by STM

Lock-and-key effect in the surface diffusion of large organic molecules probed by STM

Zwitterionic self-assembly of l -methionine nanogratings on the Ag(111) surface

Two-Dimensional Nanotemplates as Surface Cues for the Controlled Assembly of Organic Molecules

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