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(a) Chemical structure of perylene-3,4,9,10-tetracarboxylic diimide (PTCDI). (b) STM image of an extended PTCDI island formed on a Au(111) terrace (I t = 0.41 nA, V t = 1.25 V). (c) Highresolution STM image of the PTCDI structure (I t = 0.41 nA, V t = 1.25 V). (d) Optimized model of close-packed PTCDI arrangement on Au(111) after full relaxation with the MM4 force-field method, revealing that PTCDI are aligned into rows in a head-to-tail style by intermolecular double hydrogen bonding (Au atoms are represented by yellow balls). (e) STM image of monolayer-height Ni clusters at a coverage of ~0.05 ML nucleated at the elbow sites of the Au(111) herringbone reconstruction (I t = 0.38 nA, V t = 1.25 V)
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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 synt...
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... this study, we investigate metal-organic self- assembly of perylene-3,4,9,10-tetracarboxylic diimide (PTCDI, see Fig. 1(a)) and Ni on the Au(111) surface using high-resolution STM under ultrahigh vacuum (UHV) conditions. The molecule PTCDI and its derivatives are technologically relevant owing to their interesting opto-electronic properties [40,41], and their adsorption properties have been investigated on a wide range of substrates ...
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... of the molecules is rotated slightly (~12°) with respect to the direction of the molecular rows. The herringbone reconstruction of the Au(111) substrate is not signifi- cantly perturbed by the adsorption of the PTCDI molecules, as judged from a characteristic modulation of the molecular corrugation clearly observed in large scale images, e.g., in Fig. ...
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... the outermost lattice plane of the substrate and the plane formed by the central benzene ring). These results are consistent with previous calculations for perylenetetracarboxylic dianhydride (PTCDA), a close analog of PTCDI [62]. A model for the extended PTCDI structure on the Au(111) surface was obtained from MM4 calculations and is shown in Fig. 1(d): Starting with a molecular arrangement involving molecules in the optimum atop positions, one finds after full relaxation an alignment into rows, allowing for double N-HO H-bonding interaction between the imide and carboxyl groups of neighbouring PTCDI molecules along the rows. The calculated structure has a unit cell size of ...
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... axis and the row axis is 12.2° 0.5°, and approximately 12° between the row axis and the [110] direction of the sur- face, all consistent with the experimental observations. In order to validate the MM4 H-bonding parameteriza- tion, we have checked the double N-HO H-bonding in the head-to-tail configuration of two PTCDI molecules, as shown in Fig. 1(d), which can be accurately described from ab initio calculations at the SCF-MP2 (TZVP) level with the GAMESS code [53]. The bond length between two molecules, that is to say the N-HO distance, is 2.64 Å in agreement with the full structural model. The stabilization energy is -0.41 eV for two molecules joined by double N-HO hydrogen ...
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... of Ni atoms alone leads to isolated Ni clusters, as shown in the STM image of Fig. 1(e). The Ni atoms were deposited at a coverage of ~0.05 ML (ML = monolayer) on an Au(111) substrate kept at room temperature, followed directly by cooling to 110 K without post-deposition annealing. The Ni clusters have an average size of 3.0 nm and are found exclusively at the bulged elbow sites of the Au (111) herringbone ...
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... 2.5 Å.) The Ni adatom is surrounded by three PTCDI molecules calculated to be somewhat further away from the surface at a height of 3.80 Å. In this configuration, each PTCDI molecule has the two oxygen atoms on one side of the molecular axis pointing towards the central Ni atom. However, the NiO distances, which fall in two classes as seen in Fig. 2(c) d 1 = 6.75 ± 0.08 Å and d 2 = 8.56 ± 0.03 Å, are much too large to allow for significant electron cloud overlapping between the Ni and O atoms. To assess a possible contribution from electrostatic interactions, accurate PM6 calculations were performed to obtain the Mulliken partial charges on every atomic site of the MM4 optimized structure. ...
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... Many works have shown that permanent charges on molecules with ionic character generate electronic interactions that influence the formation of molecular structures on surfaces with alternate anions and cations [5,[49][50][51]. In 2012, the Miao Yu group characterized the self-assembly of PTCDI molecules (perylene-3,4,9,10-tetracarboxylic diimide), C 12 N 2 H 10 O 4 , along with Ni atoms on a metallic substrate, using a combination of STM measurements and simulated STM images with the EHMO-ESQC method [37][38][39][40][41]52]. After optimizing the systems on the substrate with the molecular mechanics MM4(2003) code [36], to establish the nanostructures on the surface, they demonstrated that it is possible to synthesize different types of nanostructures (Figure 9), such as zero-dimensional (0D) structures involving three PTCDI molecules assembled primarily by vdW interactions and weak HBs surrounding a central Ni atom (Figure 9b,f,j), one-dimensional (1D) chains of PTCDI molecules linked by double N − H · · · O HBs (3.3 Å), with each molecule surrounded by four Ni atoms near CDI groups (Figure 9a,e,i), and the two-dimensional (2D) network, as displayed in Figure 9d,h. ...
The bottom-up fabrication of supramolecular and self-assembly on various substrates has become an extremely relevant goal to achieve prospects in the development of nanodevices for electronic circuitry or sensors. One of the branches of this field is the self-assembly of functional molecular components driven through non-covalent interactions on the surfaces, such as van der Waals (vdW) interactions, hydrogen bonding (HB), electrostatic interactions, etc., allowing the controlled design of nanostructures that can satisfy the requirements of nanoengineering concepts. In this context, non-covalent interactions present opportunities that have been previously explored in several molecular systems adsorbed on surfaces, primarily due to their highly directional nature which facilitates the formation of well-ordered structures. Herein, we review a series of research works by combining STM (scanning tunneling microscopy) with theoretical calculations, to reveal the processes used in the area of self-assembly driven by molecule Landers equipped with functional groups on the metallic surfaces. Combining these processes is necessary for researchers to advance the self-assembly of supramolecular architectures driven by multiple non-covalent interactions on solid surfaces.
... The EDA-PTCDA photocatalyst was synthesized via the amide base condensation reaction between EDA and PTCDA under solvothermal conditions (Figure 1a and Scheme S1). [11,12] The successful self-assembly of amino monomers and anhydride groups to form CN bonds was confirmed by X-ray diffraction (XRD) and Fourier infrared spectroscopy (FT-IR) results ( Figure S2a-b). The flexibility of the CÀ C bond of EDA leads to low crystallinity of EDA-PTCDA, and the wide peak at 25.11°indicates a weak π-π stacking structure. ...
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... Surface-confined supramolecular chemistry has emerged as a powerful approach toward precise fabrication of low-dimensional nanomaterials. 1 The molecular building blocks in a supramolecular system can be stabilized by diverse noncovalent intermolecular interactions 2 such as hydrogen 3 and halogen 4−7 bonds, electrostatic 8,9 and dipole−dipole 10,11 interactions, coordination, 12−14 and so forth. Normally, these intermolecular interactions are so weak that slight structural changes in the molecular building blocks or appearance and variation of substrate surfaces may alter the supramolecular structures. ...
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... However, the adsorption distances of the atoms in the functional groups differ notably and the ELA is considerably different: the energylevels of PTCDA are Fermi level pinned on the (111)-surfaces of noble metals [75] and virtually all substrates [128], whereas for PTCDI the ELA is vacuum-level controlled [80]. The coupling of PTCDA (and to minor extent also of PTCDI) to metals has been subject to extensive research (see references [18,75,80,148,150,407,430,433,[535][536][537][538][539][540][541][542][543] as well as the review papers [83,85,432]). ...
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... However, the adsorption distances of the atoms in the functional groups differ notably and the ELA is considerably different: the energylevels of PTCDA are Fermi level pinned on the (111)-surfaces of noble metals [75] and virtually all substrates [128], whereas for PTCDI the ELA is vacuum-level controlled [80]. The coupling of PTCDA (and to minor extent also of PTCDI) to metals has been subject to extensive research (see references [18,75,80,148,150,407,430,433,[535][536][537][538][539][540][541][542][543] as well as the review papers [83,85,432]). ...
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The formation of highly organized structures based on two ligands with pyridyl functionalities, 4,4'-bipyridine (BPY) and 1,4-di(4,4"-pyridyl) benzene (BPYB)), and Cu adatoms on the Cu(111) surface has been studied with low temperature and variable temperature scanning tunneling microscopy (STM) and first-principle calculations. We are showing that the formation of a highly organized adlayer built from adatom-molecule and molecule-molecule units strongly depends on the amount of mobile Cu atoms on the surface. While a high concentration of Cu adatoms (high adatom/BPY ratio, ≥ 1) leads systematically to the formation of organometallic nanolines, the absence of them (low adatom/BPY ratio, ≈ 0) gives compact self-assembled molecular network, and more specifically hydrogen-bond networks (HBN) with BPY molecules organized in a T-shaped fashion. Alternatively, an intermediate concentration of Cu adatoms (0 < adatom/BPY < 1) allows the formation of a well-organized and compact structure where both organometallic and HBN components coexist. Although STM images cannot clearly reveal the presence of Cu adatom within the organometallic moiety, the bonding of BPY to a single or two Cu adatoms can be clearly identified by tunneling spectroscopy (STS), and is supported by Density Functional Theory (DFT) results. Additional STM simulations suggest that the relative position of the Cu adatom with respect to organic ligands just above has a significant impact on its detection by STM. This study exemplifies the prominent role of metallic adatoms on the formation of complex organometallic network and should open more rational practices to optimize the formation of those supramolecular networks.
... adapted to provide a molecules. 35,36 Thes contributor to the − occupied molecular unoccupied molecu resonance. Those im optimized f lat BBD co confirms how the B conformation by STM to Figure 5 images, electronically decoupl ...
The molecular conformation of a bisbinaphthyldurene (BBD) molecule is manipulated using an LT-UHV STM on an Au(111) surface. BBD has two binaphthyl groups at both ends connected to a central durene leading to anti/syn/flat conformers. In solution, dynamic NMR indicated the fast interexchange between the anti and syn conformers as confirmed by DFT calculations. After deposition in a sub-monolayer on an Au(111) surface, only the syn conformers were observed forming small islands of self-assembled syn dimers. The syn dimers can be separated in 2 syn monomers by STM molecular manipulations. A flat conformer can also be prepared but using a peculiar mechanical unfolding of a syn monomer by STM manipulations. The experimental STM dI/dV and theoretical ESQC maps of the low lying tunneling resonances confirmed the flat conformer BBD molecule STM production. The key BBD electronic states for a step by step STM inelastic excitation lateral motion on the Au(111) are presented requiring no mechanical interactions between the STM tip apex and the BBD. On the BBD molecular board, selected STM tip apex positions for this inelastic tunneling excitation enable the flat BBD to move controllably on Au(111) by step of 0.29 nm per bias voltage ramp.
... As an example, codeposition of Ni atoms and perylene tetracarboxylic diimide (PTCDI) molecules produces three distinct types of nanostructures as a function of the Ni-PTCDI coverage. 173 Here, the Ni adatoms acquire a negative partial charge through interaction with the substrate, and the Ni-PTCDI interaction is entirely electrostatic, which is consistent with the 18-electron rule for transition metal complexes. 174 A surface coordination network involving negatively charged metal centers was reported 175 in the case of Cu/Cu(111), in which it was shown that a Cu adatom surrounded by three 9,10anthracenedicarbonitrile molecules exhibits an excess of negative partial charge to remedy electron donation from the substrate to the ligand. ...
This review aims at giving the readers the basic concepts needed to understand two-dimensional bimolecular organizations at the vacuum-solid interface. The first part describes and analyzes molecules-molecules and molecules-substrates interactions. The current limitations and needs in the understanding of these forces are also detailed. Then, a critical analysis of the past and recent advances in the field is presented by discussing most of the key papers describing bicomponents self-assembly on solid surface in an ultrahigh vacuum environment. These sections are organized by considering decreasing molecule-molecule interaction strengths (i.e. starting from strong directional multiple H bonds up to weaker nondirectional bonds taking into account the increasing fundamental role played by the surface). Finally, we conclude with some research directions (predicting self-assembly, multi-components systems, and nonmetallic surfaces) and potential applications (porous networks and organic surfaces).
... We have seen in Chapter 3 that PTCDI molecules spontaneously form H-bonded self-assembled organic films on Au (111) surface. Depending on the preparation conditions, adding metal adatoms on the surface will lead to totally different nanoarchitectures stabilized by metalorganic arrangement [153,154]. As a comparison, the strength of the ionic bond can be ten times higher than H-bond interactions [155]. ...
Over the last few years, important technological developments were made following a trend towards miniaturization. In particular, lots of research efforts are put into the research on organic electronics and on 2D materials like graphene. Such 2D materials show great physical properties and are promising candidates for the development of future electronic devices.In this project, bottom-up approach consisting in assembling elementary building blocks together, was used to engineer novel twodimensional nanostructures on metal surfaces. The properties of these two-dimensional nanostructures were investigated using Scanning Tunneling Microscopy (STM) and X-ray Photoemission Spectroscopy (XPS). Two-dimensional nanostructures based on the self-assembly of organic building blocks stabilized by intermolecular interactions were engineered. In particular, nanostructures stabilized by hydrogen bonds, halogen bonds and ionic-organic interactions were investigated. Localized electronic states due to specific molecular lateral electronic coupling were observed. Four different ionic-organic nanoarchitectures were engineered varying the substrate temperature. Covalent organic nanostructures were also engineered by onsurface Ullmann coupling reaction. Two different star-shaped precursors with iodine and bromine substituents respectively, were investigated. Large periodic porous 2D covalent hexagonal carbon nanostructures weresuccessfully engineered by temperature driven hierarchal Ullmann coupling. These results open new perspectives for the development of 2D organic materials with controlled structures and properties.
