A Paradigm Shift from 2D to 3D: Surface Supramolecular Assemblies and Their Electronic Properties Explored by Scanning Tunneling Microscopy and Spectroscopy.

Exploring supramolecular architectures at surfaces plays an increasingly important role in contemporary science, especially for molecular electronics. A paradigm of research interest in this context is shifting from 2D to 3D that is expanding from monolayer, bilayers, to multilayers. Taking advantage of its high-resolution insight into monolayers and a few layers, scanning tunneling microscopy/spectroscopy (STM/STS) turns out a powerful tool for analyzing such thin films on a solid surface. This review summarizes the representative efforts of STM/STS studies of layered supramolecular assemblies and their unique electronic properties, especially at the liquid-solid interface. The superiority of the 3D molecular networks at surfaces is elucidated and an outlook on the challenges that still lie ahead is provided. This review not only highlights the profound progress in 3D supramolecular assemblies but also provides researchers with unusual concepts to design surface supramolecular structures with increasing complexity and desired functionality.

STM Study of the Self-Assembly of Biphenyl-3,3',5,5'-Tetracarboxylic Acid and Its Mixing Behavior with Coronene at the Liquid-Solid Interface.

We report a scanning tunneling microscopy (STM) study of the molecular self-assembly of biphenyl-3,3',5,5'-tetracarboxylic acid (BPTC) at the octanoic acid/graphite interface. STM revealed that the BPTC molecules generated stable bilayers and monolayers under high and low sample concentrations, respectively. Besides hydrogen bonds, the bilayers were stabilized by molecular π-stacking, whereas the monolayers were maintained by solvent co-adsorption. A thermodynamically stable Kagomé structure was obtained upon mixing BPTC with coronene (COR), while kinetic trapping of COR in the co-crystal structure was found by the subsequent deposition of COR onto a preformed BPTC bilayer on the surface. Force field calculation was conducted to compare the binding energies of different phases, which helped to provide plausible explanations for the structural stability formed via kinetic and thermodynamic pathways.

Odd-Even Effect on Supramolecular Co-Assemblies: Control over the Two-Dimensional Self-Assemblies of a Fluorenone Derivative with Asymmetrically Substituted Alkyl Chains.

The precise control of two-dimensional supramolecular co-assemblies presents a research topic related to advance nanotechnology. Here, we report a scanning tunneling microscopy (STM) study of the mixture behavior of three fluorenone derivatives at the liquid-solid interface. The target molecule is F-C12C13 whose structure bears asymmetrical alkyls, whereas the regulating molecules, either F-C12C12 or F-C13C13, are structurally symmetric. By STM imaging of systematic mixtures with various volumes among the sample solutions, we found that the mixing ratio mainly determined the binary outcomes. Compared with F-C12C12, F-C13C13 shows a stronger ability to dominate the patterning, explained by the larger binding and adsorption energies calculated by the force field simulations. Moreover, the odd-even effect exists in the system. Overall, we acquired knowledge about the regulating ability of bi-component supramolecular assembling, especially for structurally asymmetric molecular systems.

Supramolecular Chemistry: Host-Guest Molecular Complexes.

In recent times, researchers have emphasized practical approaches for capturing coordinated and selective guest entrap. The physisorbed nanoporous supramolecular complexes have been widely used to restrain various guest species on compact supporting surfaces. The host-guest (HG) interactions in two-dimensional (2D) permeable porous linkages are growing expeditiously due to their future applications in biocatalysis, separation technology, or nanoscale patterning. The different crystal-like nanoporous network has been acquired to enclose and trap guest molecules of various dimensions and contours. The host centers have been lumped together via noncovalent interactions (such as hydrogen bonds, van der Waals (vdW) interactions, or coordinate bonds). In this review article, we enlighten and elucidate recent progress in HG chemistry, explored via scanning tunneling microscopy (STM). We summarize the synthesis, design, and characterization of typical HG structural design examined on various substrates, under ambient surroundings at the liquid-solid (LS) interface, or during ultrahigh vacuum (UHV). We emphasize isoreticular complexes, vibrant HG coordination, or hosts functional cavities responsive to the applied stimulus. Finally, we critically discuss the significant challenges in advancing this developing electrochemical field.

Monolayer and Bilayer Formation of Molecular 2D Networks Assembled at the Liquid/Solid Interfaces by Solution-Based Drop-Cast Method.

In recent years, extending self-assembled structures from two-dimensions (2D) to three-dimensions (3D) has been a paradigm in surface supramolecular chemistry and contemporary nanotechnology. Using organic molecules of p-terphenyl-3,5,3',5'-tetracarboxylic acid (TPTC), and scanning tunneling microscopy (STM), we present a simple route, that is the control of the solute solubility in a sample solution, to achieve the vertical growth of supramolecular self-assemblies, which would otherwise form monolayers at the organic solvent/graphite interface. Presumably, the bilayer formations were based on π-conjugated overlapped molecular dimers that worked as nuclei to induce the yielding of the second layer. We also tested other molecules, including trimesic acid (TMA) and 1,3,5-tris(4-carboxyphenyl)-benzene (BTB), as well as the further application of our methodology, demonstrating the facile preparation of layered assemblies.

Synergic Effect: Temperature-Assisted Electric-Field-Induced Supramolecular Phase Transitions at the Liquid/Solid Interface.

Using trimesic acid (TMA) as a model system by means of scanning tunneling microscope (STM) equipped with a temperature controller, here, we report a temperature-assisted method to cooperatively control electric-field-induced supramolecular phase transitions at the liquid/solid interface. Octanoic acid is used as a solvent due to its good solubility for TMA and its less complicated pattern formed under negative STM bias (e.g., only chicken-wire polymorphs existing). At positive substrate bias, STM revealed that TMA assembly based on temperature modulations underwent phase transitions from a porous (22 °C) to a flower (45 °C) and further to a zigzag (68 °C) structure. The transitions are ascribed to the partial deprotonation of the carboxyl groups of TMA. Both the temperature and electrical polarity of the substrate are crucial, i.e., the transitions only take place at positive substrate bias and elevated temperatures. Molecular mechanics simulations were carried out to calculate the temperature and electric field dependence of the adsorption enthalpy and free energy of the chicken-wire assembly of TMA on the two layers of graphene surface. The calculated decrease in adsorption enthalpy with the increase of temperature and electric field values that causes the TMA chicken-wire assembly to be less stable is proposed to promote the occurrence of the phase transition observed by STM. This study paves the way toward program-controlled supramolecular phase switching via the synergic effect of electrical and thermal stimuli.

Hydrophobic surface modified HfO2 antireflective coatings.

A multifunctional antireflective (AR) thin film is always a prerequisite for growing high-tech applications. Herein we proposed a surface modification technique to transform the hydrophilic behaviour of HfO2 AR nanofilms into hydrophobic without influencing the nanostructure, morphology, refractive index (η) or AR efficacy of HfO2 nanofilms. Our experimental results demonstrate that the fabricated HfO2 AR nanofilms retain its AR efficiency after surface modification to <1% in the visible wavelength range (450-700 nm) on FTO and sapphire. HfO2 AR nanofilms show hydrophilic behaviour before surface modification with a water contact angle (WCA) of 29° on FTO and 22° on sapphire. However, after surface treatment, they display hydrophobic nature θ w > Î¸ > 90° with a contact angle of (127°-130°). The experimental result demonstrates that the η of the thin layers fabricated at deposition angle 0°, 80°, and 88° before and after modification remains almost the same. HfO2 AR nanofilms exhibit long term AR permanency as AR efficiency measured within a year practically displays the equivalent reflectance curves similar to as deposit AR thin films, i.e. <1% in the wavelength range of 450-700 nm. We proposed a cost-effective procedure to make hydrophilic AR films to show non-wetting behaviour for its long-term exposure in a moist, damp environment without affecting the refractive index of AR thin film.

Template-Assisted Proximity for Oligomerization of Fullerenes.

Demonstrated herein is an unprecedented porous template-assisted reaction at the solid-liquid interface involving bond formation, which is typically collision-driven and occurs in the solution and gas phases. The template is a TMA (trimesic acid) monolayer with two-dimensional pores that host fullerenes, which otherwise exhibit an insignificant affinity to an undecorated graphite substrate. The confinement of C84 units in the TMA pores formulates a proximity that is ideal for bond formation. The oligomerization of C84 is triggered by an electric pulse via a scanning tunneling microscope tip. The spacing between C84 moieties becomes 1.4 nm, which is larger than the edge-to-edge diameter of 1.1-1.2 nm of C84 due to the formation of intermolecular single bonds. In addition, the characteristic mass-to-charge ratios of dimers and trimers are observed by mass spectrometry. The experimental findings shed light on the active role of spatially tailored templates in facilitating the chemical activity of guest molecules.

The Cyclic Hydrogen-Bonded 6-Azaindole Trimer and its Prominent Excited-State Triple-Proton-Transfer Reaction.

The compound 6-azaindole undergoes self-assembly by formation of N(1)-H⋅⋅⋅N(6) hydrogen bonds (H bonds), forming a cyclic, triply H-bonded trimer. The formation phenomenon is visualized by scanning tunneling microscopy. Remarkably, the H-bonded trimer undergoes excited-state triple proton transfer (ESTPT), resulting in a proton-transfer tautomer emission maximized at 435 nm (325 nm of the normal emission) in cyclohexane. Computational approaches affirm the thermodynamically favorable H-bonded trimer formation and the associated ESTPT reaction. Thus, nearly half a century after Michael Kasha discovered the double H-bonded dimer of 7-azaindole and its associated excited-state double-proton-transfer reaction, the triply H-bonded trimer formation of 6-azaindole and its ESTPT reaction are demonstrated.

Multicomponent self-assembly with a shape-persistent N-heterotriangulene macrocycle on Au(111).

Multicomponent network formation by using a shape-persistent macrocycle (MC6) at the interface between an organic liquid and Au(111) surface is demonstrated. MC6 serves as a versatile building block that can be coadsorbed with a variety of organic molecules based on different types of noncovalent interactions at the liquid-solid interface. Scanning tunneling microscopy (STM) reveals the formation of crystalline bicomponent networks upon codeposition of MC6 with aromatic molecules, such as fullerene (C60) and coronene. Tetracyanoquinodimethane, on the other hand, was found to induce disorder into the MC6 networks by adsorbing on the rim of the macrocycle. Immobilization of MC6 itself was studied in two different noncovalently assembled host networks. MC6 assumed a rather passive role as a guest and simply occupied the host cavities in one network, whereas it induced a structural transition in the other. Finally, the central cavity of MC6 was used to capture C60 in a complex three-component system. Precise immobilization of organic molecules at discrete locations within multicomponent networks, as demonstrated here, constitutes an important step towards bottom-up fabrication of functional surface-based nanostructures.

Flow-assisted 2D polymorph selection: stabilizing metastable monolayers at the liquid-solid interface.

Controlling crystal polymorphism constitutes a formidable challenge in contemporary chemistry. Two-dimensional (2D) crystals often provide model systems to decipher the complications in 3D crystals. In this contribution, we explore a unique way of governing 2D polymorphism at the organic liquid-solid interface. We demonstrate that a directional solvent flow could be used to stabilize crystalline monolayers of a metastable polymorph. Furthermore, flow fields active within the applied flow generate millimeter-sized domains of either polymorph in a controlled and reproducible fashion.

Forced to align: flow-induced long-range alignment of hierarchical molecular assemblies from 2D to 3D.

Nanostructured molecular thin films adsorbed on solid surfaces form the basis of numerous applications. Long-range order within adsorbed molecules is very often a desirable property for such systems. In this contribution, we report a simple and efficient method to fabricate well-aligned thin films of organic molecules over a few millimeter squares. The strategy involves use of capillary force in a two-step flow method to induce large-area alignment of multilayers of molecules at the organic liquid-solid interface. Furthermore, we also demonstrate the influence of alignment on the electron transport through these well-aligned thin films using scanning tunneling spectroscopy.

Processable Rylene Diimide Dyes up to 4 nm in Length: Synthesis and STM Visualization.

Long and planar: Facile syntheses of soluble hexarylene diimides (HDI) and octarylene diimides (ODI) are described. They are stable in both solution and the solid state and exhibit broad and intense NIR absorption. Scanning tunneling microscopy (STM) reveals that HDI, after deposition from solution, forms a unique herringbone bilayer or stable multilayers depending on the concentration.

Surface supramolecular assemblies tailored by chemical/physical and synergistic stimuli: a scanning tunneling microscopy study.

Supramolecular self-assemblies formed by various non-covalent interactions can produce diverse functional networks on solid surfaces. These networks have recently attracted much interest from both fundamental and application points of view. Unlike covalent organic frameworks (COFs), the properties of the assemblies differ from each other depending on the constituent motifs. These various motifs may find diverse applications such as in crystal engineering, surface modification, and molecular electronics. Significantly, these interactions between/among the molecular tectonics are relatively weak and reversible, which makes them responsive to external stimuli. Moreover, for a liquid-solid-interface environment, the dynamic processes are amenable to in situ observation using scanning tunneling microscopy (STM). In the literature, most review articles focus on supramolecular self-assembly interactions. This review summarizes the recent literature in which stimulation sources, including chemical, physical, and their combined stimuli, cooperatively tailor supramolecular assemblies on surfaces. The appropriate design and synthesis of functional molecules that can be integrated on different surfaces permits the use of nanostructured materials and devices for bottom-up nanotechnology. Finally, we discuss synergic effect on materials science.

Template-assisted assembly: scanning tunneling microscopy study of solvent-dependent adlattices of alkyl-derivatized tetrathiafulvalene.

The self-assembly of an adsorbate as a function of the strength of solvent-substrate adsorption is an important yet relatively unexplored subject. In this study, how the strength of solvent-substrate adsorption and solvent-solvent attraction affects the assembly of tetrakis(octadecylthio)tetrathiafulvalene (1) is scrutinized by scanning tunneling microscopy (STM). For solvents with strong intermolecular interactions and adsorption onto graphite, such as long n-alkanes (C(n)H(2n+2), n ≥ 13), STM reveals that the solvent molecules form lamellae which become a template to direct the assembly of 1 into one-dimensional arrays. The lengths of one of the unit cell vectors for the assemblies are increased and well correlated with the solvent sizes. In situ STM monitoring of 1 introduced onto graphite with preadsorbed n-tetradecane adlattices shows that the developed assemblies of 1 have striped features aligned parallel to the underlying template. In contrast, for solvents with weak adsorption, such as short n-alkanes (C(n)H(2n+2), n ≤ 12), toluene, and 1,2,4-trichlorobenzene, the adlattice structures of 1 are solvent-independent.

Double stranded polymeric ladderphanes with 16-π-electron antiaromatic metallocycle linkers.

Three double stranded polymeric ladderphanes with 16-π-electron antiaromatic metallocycle linkers are synthesised by ring opening metathesis polymerisation of the corresponding bisnorbornene monomers. Scanning tunnelling microscopic (STM) images indicate that these polymers can assemble nicely on a graphite surface to form a highly ordered pattern which has been observed in other ladderphanes with different kinds of aromatic linkers. Little change in (1)H NMR, absorption spectra and electrochemical oxidation potential between these polymers and the corresponding monomers suggest that there would be no interactions between adjacent antiaromatic linkers in these polymeric ladderphanes. Presumably, the distance between two antiaromatic rings in these ladderphanes (5-6 Å) is far too long in comparison with that between two rings in methylene-bridged antiaromatic superphanes (2.5 Å<), where stabilisation is predicted by theoretical calculations.

Flow-induced-crystallization: tailoring host-guest supramolecular co-assemblies at the liquid-solid interface.

Here, we report that using the method of simply contacting a sample solution droplet with a piece of tissue paper can create a solvent flow (capillary force). During this process, the dynamics and solvent removal can promote the formation and stabilization of a meta-stable linear quasi-crystal composed of p-terphenyl-3,5,3',5'-tetracarboxylic acid (TPTC) molecules, which would otherwise pack into thermodynamically favored random tiling. The tailored quasi-crystal (linear) template allows atop it higher-efficiency accommodation of fullerene molecules (C60) from 40.1% to 97.5%, compared with that obtained in the random-tiling (porous) case. Overall, the result of this study presents an unusual yet remarkably simple strategy for tailoring complex host-guest supramolecular systems at the liquid-solid interface.

An Assessment of MXenes through Scanning Probe Microscopy.

Recently, exploring the unique properties of 2D materials has constituted a new wave of research, which lead these materials to enormous applications ranging from optoelectronics to healthcare systems. Due to the profusion of surface terminated functionalities, MXenes have become an emerging class of 2D materials that can be easily integrated with other materials. The versatility of MXenes allows to tune their finest material properties for further device applications. This review initiates with the classification of preparation methods of MXenes, where the authors elaborate on the significance of top-down approaches including the exfoliation of solid layers. Next, the focus is diverted toward the materials analysis of MXenes including their terminations analysis as well as their intriguing electrical and mechanical behaviors through scanning probe microscopy. Finally, critical challenges and perspectives for MXenes analysis and applications are explored and discussed. Therefore, this comprehensive review can encourage researchers, and offer a precise direction to employ MXenes in various applications.

Gearing of molecular swirls: columnar packing of nematogenic hexakis(4-alkoxyphenylethynyl)benzene derivatives.

Through molecular design and straightforward synthesis, incorporating an additional alkoxy chain onto various numbers of peripheral phenyls in nematogenic hexakis(4-alkoxyphenylethynyl)benzene was achieved to generate columnar phases with significantly expanded temperature ranges. For the compound with two decyloxy chains on every peripheral phenyl, scanning tunnelling microscopic studies indicate the molecule adopts a preferred molecular-swirl geometry by restricting the conformational arrangement of the alkoxy side chains. Cooperative packing of the molecular swirls by a lock-in mechanism among columns results in a stable helical column packing evidenced by powder X-ray diffraction.

Substrate Impact on MR Characteristics of Carbon Nano Films Explored via AFM and Raman Analysis.

Recent advances in the fabrication and classification of amorphous carbon (a-Carbon) thin films play an active part in the field of surface materials science. In this paper, a pulsed laser deposition (PLD) technique through controlling experimental parameters, including deposition time/temperature and laser energy/frequency, has been employed to examine the substrate effect of amorphous carbon thin film fabrication over SiO2 and glass substrates. In this paper, we have examined the structural and magnetoresistance (MR) properties of these thin films. The intensity ratio of the G-band and D-band (ID/IG) were 1.1 and 2.4, where the C(sp2) atomic ratio for the thin films samples that were prepared on glass and SiO2 substrates, were observed as 65% and 85%, respectively. The MR properties were examined under a magnetic field ranging from -9 T to 9 T within a 2-K to 40-K temperature range. A positive MR value of 15% was examined at a low temperature of 2 K for the thin films grown on SiO2 substrate at a growth temperature of 400 °C using a 300 mJ/pulse laser frequency. The structural changes may tune the magnetoresistance properties of these a-Carbon materials. These results were demonstrated to be highly promising for carbon-based spintronics and magnetic sensors.