Self-assembled Molecular Network Research Articles

Defect-engineered surfaces to investigate the formation of self-assembled molecular networks.

Herein we report the impact of covalent modification (grafting), inducing lateral nanoconfinement conditions, on the self-assembly of a quinonoid zwitterion derivative into self-assembled molecular networks at the liquid/solid interface. At low concentrations where the compound does not show self-assembly behaviour on bare highly oriented pyrolytic graphite (HOPG), close-packed self-assembled structures are visualized by scanning tunneling microscopy on covalently modified HOPG. The size of the self-assembled domains decreases with increasing the density of grafted molecules, i.e. the molecules covalently bound to the surface. The dynamics of domains are captured with molecular resolution, revealing not only time-dependent growth and shrinkage processes but also the orientation conversion of assembled domains. Grafted pins play a key role in initiating the formation of on-surface molecular self-assembly and their stabilization, providing an elegant route to study various aspects of nucleation and growth processes of self-assembled molecular networks.

Doping of graphene via adlayer formation of electrochemically reduced dibenzyl viologen

Doping of graphene by self-assembled molecular network of uncharged dibenzyl viologen (DBV0) generated in situ.

Self-assembled molecular network formed by controlling molecular deposition of organic compounds

Self-assembled molecular networks enable spatial and temporal control of surface chemical functionalities. However, in most cases, the deposition process is unsuitable to the growth of multilayers. In this study, we attempted the consecutive deposition of a two-dimensional supramolecular array on another to fabricate an organic layer (OL) and realize the growth mechanism on underlying inorganic layer of distinct ordered layers, each of which is stabilized by in-plane non-covalent bonds. An OL was formed by depositing pyromellitic acid (PMA) through ultrahigh-vacuum physical vapor deposition on a metal-oxide and metal-aluminate system tailored by plasma electrolytic oxidation, and the unique interface between the organic and inorganic layers was characterized by field-emission transmission electron microscopy under ambient conditions. The adsorption behavior of pyromellitic acid (PMA) on the inorganic surface was investigated by computational calculations. The adsorption of PMA over an inorganic surface was more favorable than the adsorption between PMA molecules themselves.

Detection and Stabilization of a Previously Unknown Two-Dimensional (Pseudo)polymorph using Lateral Nanoconfinement.

We report on the detection and stabilization of a previously unknown two-dimensional (2D) pseudopolymorph of an alkoxy isophthalic acid using lateral nanoconfinement. The self-assembled molecular networks formed by the isophthalic acid derivative were studied at the interface between covalently modified graphite and an organic solvent. When self-assembled on graphite with moderate surface coverage of covalently bound aryl groups, a previously unknown metastable pseudopolymorph was detected. This pseudopolymorph, which was presumably "trapped" in between the surface bound aryl groups, underwent a time-dependent phase transition to the stable polymorph typically observed on pristine graphite. The stabilization of the pseudopolymorph was then achieved by using an alternative nanoconfinement strategy, where the domains of the pseudopolymorph could be formed and stabilized by restricting the self-assembly in nanometer-sized shallow compartments produced by STM-based nanolithography carried out on a graphite surface with a high density of covalently bound aryl groups. These experimental results are supported by molecular mechanics and molecular dynamics simulations, which not only provide important insight into the relative stabilities of the different structures, but also shed light onto the mechanism of the formation and stabilization of the pseudopolymorph under nanoscopic lateral confinement.

Two-Dimensional Molecular Network Built from Hierarchy Self-Assembly of Perylene Bisimide Derivatives.

The structures of two-dimensional (2D) self-assembled molecular networks formed by a series of perylene bisimide (PBI) derivatives were investigated by scanning tunneling microscopy (STM). By introducing different functional groups to the PBI rings, we successfully built a different self-assembled molecular network on the liquid-solid interface. When the substituent is propanol, PBI is aligned in lines. When we introduced either an ester group or an amide group to the PBI compounds, they tended to form dimers and trimers. Especially, the PBI with the amide groups can form a 2D porous molecular network by hierarchy self-assembly. The 2D porous molecular network has a great potential to be the host molecule for the accommodation of a guest molecule, coronene (COR), and the structure of the 2D porous molecular network can be tuned by varying the concentration. The density functional theory calculations were also performed to disclose the mechanisms involved.

"Concentration-in-Control" self-assembly concept at the liquid-solid interface challenged.

Self-assembled molecular networks (SAMNs) on surfaces evoke a lot of interest, both from a fundamental as well as application point of view. When formed at the liquid–solid interface, precise control over different polymorphs can be achieved by simply adjusting the concentration of molecular building blocks in solution. Significant influence of solute concentration on self-assembly behavior has been observed, whether the self-assembly behavior is controlled by either van der Waals forces or hydrogen bonding interactions. In both cases, high- and low-density supramolecular networks have been observed at high and low solute concentrations, respectively. In contrast to this “concentration-in-control” self-assembly concept here we report an atypical concentration dependent self-assembly behavior at a solution–solid interface. At the interface between heptanoic acid (HA) and highly oriented pyrolytic graphite (HOPG), we show, using scanning tunneling microscopy (STM), the formation of a low-density porous network at high solute concentrations, and a high-density compact network at low solute concentrations. This intriguing inverse concentration dependent self-assembly behavior has been attributed to the preaggregation of solute molecules in the heptanoic acid solution as revealed by UV-vis spectroscopy. The observed results have been correlated to the molecular density of self-assembled monolayers attained at the HA/HOPG interface.

Molecular dopant determines the structure of a physisorbed self-assembled molecular network.

A small percentage of an impurity was shown, via scanning tunneling microscopy, to drastically change the on-surface self-assembly behavior of an aromatic tetracarboxylic acid, by initiating the nucleation and growth of a different polymorph. Molecular modelling simulations were used to shed further light onto the dopant-controlled assembly behaviour.

2D Self-assembled molecular networks and on-surface reactivity under nanoscale lateral confinement.

Supramolecular self-assembly at surfaces provides a pathway for building chemically customized interfaces. Over the last three decades, research on the role of key parameters such as temperature, solute concentration, and molecular design has enabled a steady increase in the complexity of self-assembled molecular networks (SAMNs) that can thus be created. However, the structure and quality of SAMNs is often determined during the early stages of nucleation and growth. To study and influence self-assembly processes at this deterministic length scale, spatial confinement of molecular adsorbates to well-defined surface patterns with nanoscale lateral dimensions offers exciting possibilities. The aim of this tutorial review is to give an overview of the various ways in which confinement impacts SAMN formation, and how we can use that knowledge to direct assemblies towards desired structures. The possibility to exploit confinement for improved control over on-surface reactions is also contemplated.

Porous Self-Assembled Molecular Networks as Templates for Chiral-Position-Controlled Chemical Functionalization of Graphitic Surfaces.

Controlled covalent functionalization of graphitic surfaces with molecular scale precision is crucial for tailored modulation of the chemical and physical properties of carbon materials. We herein present that porous self-assembled molecular networks (SAMNs) act as nanometer scale template for the covalent electrochemical functionalization of graphite using an aryldiazonium salt. Hexagonally aligned achiral grafted species with lateral periodicity of 2.3, 2.7, and 3.0 nm were achieved utilizing SAMNs having different pore-to-pore distances. The unit cell vectors of the grafted pattern match those of the SAMN. After the covalent grafting, the template SAMNs can be removed by simple washing with a common organic solvent. We briefly discuss the mechanism of the observed pattern transfer. The unit cell vectors of the grafted pattern align along nonsymmetry axes of graphite, leading to mirror image grafted domains, in accordance with the domain-specific chirality of the template. In the case in which a homochiral building block is used for SAMN formation, one of the 2D mirror image grafted patterns is canceled. This is the first example of a nearly crystalline one-sided or supratopic covalent chemical functionalization. In addition, the positional control imposed by the SAMN renders the functionalized surface (homo)chiral reaching a novel level of control for the functionalization of carbon surfaces, including surface-supported graphene.

Trapping a pentagonal molecule in a self-assembled molecular network: an alkoxylated isosceles triangular molecule does the job.

We herein report a unique example of on-surface adaptive self-assembly. A pentagon-shaped macrocycle, cyclic [5]meta-phenyleneacetylene [5]CMPA, is trapped by the adaptive supramolecular network formed by an isosceles triangular molecule, alkoxy substituted dehydrobenzo[14]annulene [14]ISODBA at the liquid/graphite interface, leading to a highly ordered and large-area bicomponent self-assembled molecular network (SAMN), as revealed by scanning tunneling microscopy (STM).

Hierarchical two-dimensional molecular assembly through dynamic combination of conformational states at the liquid/solid interface.

Self-sorting of multiple building blocks for correctly positioning molecules through orthogonal recognition is a promising strategy for construction of a hierarchical self-assembled molecular network (SAMN) on a surface. Herein we report that a trigonal molecule, dehydrobenzo[12]annulene (DBA) derivative having three tetradecyloxy chains and three hydroxy groups in an alternating manner, forms hierarchical triangular clusters of different sizes ranging from 2.4 to 16.4 nm, consisting of 3 to 78 molecules, respectively, at the liquid/graphite interface. The key is the dynamic combination of three different conformational states, which is solvent and concentration dependent. The present knowledge extends design strategies for production of sophisticated hierarchical SAMNs using a single component at the liquid/solid interface.

Electrostatically Driven Guest Binding in Self-Assembled Molecular Network of Hexagonal Pyridine Macrocycle at the Liquid/Solid Interface: Symmetry Breaking Induced by Coadsorbed Solvent Molecules.

We present here the construction of a self-assembled two-dimensional network at the liquid/solid interface using a hexagonal pyridine macrocycle which binds an organic cation in its intrinsic porous space by electrostatic interactions. For this purpose, a hexagonal pyridinylene-butadiynylene macrocycle (PyBM) having six octyloxymethyl groups, PyBM-C8, was synthesized. As guests, tropylium (Tr) tetrafluoroborate and trioxatriangulenium (TOTA) hexafluorophosphate were used. In this study, we focused on (i) the network patterns of PyBM-C8 which change in response to its concentration and (ii) the position of the guest immobilized in the porous space of the macrocycle. Scanning tunneling microscopy (STM) observations at the interface of 1,2,4-trichlorobenzene (TCB) and highly oriented pyrolytic graphite (HOPG) revealed that PyBM-C8 formed four different polymorphs, oblique, loose hexagonal, linear, and rectangular, depending on the solute concentration and annealing treatment. Solvent TCB molecules are likely coadsorbed to not only the intrinsically porous space of PyBM-C8 (internal TCB) but also the space outside of the macrocycle between its alkyl chains (external TCB) in most of the cases. Upon adding the guest cation, whereas small Tr was not visualized in the pore due to size mismatching, larger TOTA was clearly observed in each pore. In addition, based on high-resolution STM images of the rhombus packing pattern of PyBM-C8, we revealed experimentally that TOTA was placed at an off-center position of the deformed hexagonal macrocyclic core in the rhombus pattern. On the basis of the molecular mechanics calculations, we hypothesize that the off-center location of TOTA is due to deformation of the hexagonal macrocycle through interaction with two external TCB molecules located at opposite edges of the macrocyclic core. Symmetry breaking of the macrocyclic host framework induced by coadsorbed surrounding solvent molecules thus plays a significant role in host-guest complexation at the liquid/solid interface.

Electric-Field-Mediated Reversible Transformation between Supramolecular Networks and Covalent Organic Frameworks.

By using an oriented electric field in a scanning tunneling microscope, one can locally control the condensation of boronic acids at the liquid/solid interface. The phase transition between self-assembled molecular networks and covalent organic frameworks is controlled by changing the polarity of the applied bias. The electric-field-induced phase transformation is reversible under ambient conditions.

Reversing the Handedness of Self-Assembled Porous Molecular Networks through the Number of Identical Chiral Centres.

Scanning tunnelling microscope observations at the 1-phenyloctane/graphite interface reveal how chiral structural information at the molecular level is transferred and expressed structurally at the 2D supramolecular level for a porous system. The chirality of self-assembled molecular networks formed by chiral dehydrobenzo[12]annulene (cDBA) derivatives having three chiral chains and three achiral chains, alternatingly, is compared with those of cDBAs having six chiral chains reported previously. While for all cDBAs homochiral surfaces are formed, their handedness is not simply a reflection of the absolute configuration of the stereogenic centres. Both the number of stereogenic centres as well as the length of the achiral chains determine the supramolecular handedness, providing a deep insight into the supramolecular chirality induction mechanisms at play. Moreover, these cDBAs act to induce chirality in porous networks formed by achiral DBAs.

Mapping Conformational Changes in a Self-Assembled Two-Dimensional Molecular Network by Statistical Analysis of Conductance Images

A self-assembled two-dimensional (2D) film of tetra-phenyl-porphyrin-4-ferrocene molecules on Au(111) is studied by STM for the presence of intra- and intermolecular correlations in the configurations of the four-pendant ferrocenyl moieties. A statistical analysis of STS images exploits the Pearson’s linear correlation coefficient derived from changes in the molecular electron density across lateral positions in the molecular network as a measure of the intra- and intermolecular coupling and/or conjugation between adjacent equivalent molecular components. Density functional theory (DFT) calculation shows that these electron density changes can be assigned to conformational changes of the ferrocenyl units of the molecules. The methodology presented here can be extended to measure correlations in other 2D systems.

Phase selectivity triggered by nanoconfinement: the impact of corral dimensions.

By using a novel protocol to spatially confine molecules in well-defined small 2D areas, the so-called nanocorrals, we show using scanning tunneling microscopy (STM) how this kind of confinement affects self-assembled molecular network (SAMN) formation at a liquid-solid interface. The 2D lateral confinement, imposed by the size of the nanocorrals, has a clear impact on the phase selectivity of a molecule that can form both low-density and high-density SAMNs, the high-density phase being promoted by the confinement.

Self-Assembled Metal Molecular Networks by Nanoconfinement.

Quasi-two-dimensional (2D) metal molecular networks (MMNs) often exhibit a nanoconfinement effect and high degree of anisotropy, which are highly diverse in their mechanical, electronic, and magnetic functionalities. Here we report an interfacial self-assembly of mechanically robust 2D MMNs, in which 3d transition metals are interconnected via molecular thiol bridges. The Langmuir-Schäfer assembled freestanding 2D nanosheets exhibit highly desired anisotropic charge transport and spin susceptibility, in which light and magnetic field induced charge transfer regulates the electronic interactions. Meanwhile, the mechanistic studies involving electronic structure reveal the molecular metal packing structure-controlled nanoconfinement and charge transfer. This study opens the door to 2D ultrathin metal coordination nanostructures for emerging functional materials and devices.

Sub-molecular spectroscopy and temporary molecular charging of Ni-phthalocyanine on graphene with STM.

In this study, the self-assembled molecular network and electronic properties of Ni-phthalocyanine (NiPc) molecules on monolayer graphene (MLG)/6H-SiC(0001) were studied by room temperature Scanning Tunnelling Microscopy (STM) and Density Functional Theory (DFT) calculations. In this study, a very weak electronic coupling between the graphene and the NiPc molecules is found. This is due to the very small charge transfer of only 0.035e- per molecule. The weak molecule-graphene interaction has two observable consequences: sub-molecular resolution was obtained in the STM spectroscopy at room-temperature with the molecules adsorbed directly on the graphene, and the occupied and unoccupied molecular resonance peaks were observed to shift their position in energy as a function of the tip-surface distance. This is due to the temporary local charging (either positive or negative) that is achieved by decreasing the surface voltage under the STM tip. This may have important consequences for future studies of the opto-electronic properties of such hybrid graphene-molecule systems.

Influence of Cu adatoms on the molecular assembly of 4,4'-bipyridine on Cu(111).

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-principles calculations. We show that the formation of a highly organized adlayer built from adatom-molecule and molecule-molecule units strongly depends on the number 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, their absence (low adatom/BPY ratio, ≈0) gives a 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 adatoms within the organometallic moiety, the bonding of BPY to a single or two Cu adatoms can be clearly identified by scanning 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 the 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 a complex organometallic network and should open more rational practices to optimize the formation of these supramolecular networks.

Precise engineering of quantum dot array coupling through their barrier widths

Quantum dots are known to confine electrons within their structure. Whenever they periodically aggregate into arrays and cooperative interactions arise, novel quantum properties suitable for technological applications show up. Control over the potential barriers existing between neighboring quantum dots is therefore essential to alter their mutual crosstalk. Here we show that precise engineering of the barrier width can be experimentally achieved on surfaces by a single atom substitution in a haloaromatic compound, which in turn tunes the confinement properties through the degree of quantum dot intercoupling. We achieved this by generating self-assembled molecular nanoporous networks that confine the two-dimensional electron gas present at the surface. Indeed, these extended arrays form up on bulk surface and thin silver films alike, maintaining their overall interdot coupling. These findings pave the way to reach full control over two-dimensional electron gases by means of self-assembled molecular networks.