From One-Dimensional Disordered Racemate to Ordered Racemic Conglomerates through Metal-Coordination-Driven Self-Assembly at the Liquid-Solid Interface.

In recent years, there has been significant focus on investigating and controlling chiral self-assembly, specifically in the context of enantiomeric separation. This study explores the self-assembly behavior of 4-dodecyl-3,6-di(2-pyridyl)pyridazine (DPP-C12) at the interface between heptanoic acid (HA) and highly oriented pyrolytic graphite (HOPG) using a combination of scanning tunneling microscopy (STM) and multiscale molecular modeling. The self-assembled monolayer structure formed by DPP-C12 is periodic in one direction, but aperiodic in the direction orthogonal to it. These structures resemble 1D disordered racemic compounds. Upon introducing palladium [Pd(II)] ions, complexing with DPP-C12, these 1D disordered racemic compounds spontaneously transform into 2D racemic conglomerates, which is rationalized with the assistance of force-field simulations. Our findings provide insights into the regulation of two-dimensional chirality.

Metal Ion and Guest-Mediated Spontaneous Resolution and Solvent-Induced Chiral Symmetry Breaking in Guanine-Based Metallosupramolecular Networks.

Two-dimensional (2D) chirality has been actively studied in view of numerous applications of chiral surfaces such as in chiral resolutions and enantioselective catalysis. Here, we report on the expression and amplification of chirality in hybrid 2D metallosupramolecular networks formed by a nucleobase derivative. Self-assembly of a guanine derivative appended with a pyridyl node was studied at the solution-graphite interface in the presence and absence of coordinating metal ions. In the absence of coordinating metal ions, a monolayer that is representative of a racemic compound was obtained. This system underwent spontaneous resolution upon addition of a coordinating ion and led to the formation of a racemic conglomerate. The spontaneous resolution could also be achieved upon addition of a suitable guest molecule. The mirror symmetry observed in the formation of the metallosupramolecular networks could be broken via the use of an enantiopure solvent, which led to the formation of a globally homochiral surface.

Hydrogen-Bonded Donor-Acceptor Arrays at the Solution-Graphite Interface.

Controlling the nanoscale morphology of organic thin films represents a critical challenge in the fabrication of organic (opto)electronic devices. The morphology of the (multicomponent) thin films in turn depends on the mutual orientation of the molecular components and their supramolecular packing on the surface. Here, it is shown how the surface co-assembly of electron-donating and -accepting building blocks can be controlled via (supra)molecular design. Hexa-peri-hexabenzocoronene (HBC) derivatives with multiple hydrogen-bonding (H-bonding) sites were synthesized and their co-assembly with alkyl-substituted perylene tetracarboxy diimide (PDI) was studied using scanning tunneling microscopy (STM) at the solution-graphite interface. STM data shows that electron-rich HBCs co-assemble laterally with electron deficient PDIs via preprogrammed H-bonding sites with high fidelity. The surface stoichiometry of the two components could be readily tuned by changing the number of H-bonding sites on the HBC derivatives via organic synthesis. This model study highlights the utility of (supra)molecular design in co-assembly of building blocks relevant for organic electronics.

Adding Four Extra K-Regions to Hexa-peri-hexabenzocoronene.

A multistep synthesis of hexa-peri-hexabenzocoronene (HBC) with four additional K-regions was developed through a precursor based on two benzotetraphene units bridged with p-phenylene, featuring preinstalled zigzag moieties. Characterization by laser desorption/ionization time-of-flight mass spectrometry, Raman and IR spectroscopy, and scanning tunneling microscopy unambiguously validated the successful formation of this novel zigzag edge-rich HBC derivative. STM imaging of its monolayers revealed large-area, defect-free adlayers. The optical properties of the modified HBC were investigated by UV/visible absorption spectroscopy.

Poly(ethylene oxide) Functionalized Graphene Nanoribbons with Excellent Solution Processability.

Structurally well-defined graphene nanoribbons (GNRs) have attracted great interest as next-generation semiconductor materials. The functionalization of GNRs with polymeric side chains, which can widely broaden GNR-related studies on physiochemical properties and potential applications, has remained unexplored. Here, we demonstrate the bottom-up solution synthesis of defect-free GNRs grafted with flexible poly(ethylene oxide) (PEO) chains. The GNR backbones possess an armchair edge structure with a width of 1.0-1.7 nm and mean lengths of 15-60 nm, enabling near-infrared absorption and a low bandgap of 1.3 eV. Remarkably, the PEO grafting renders the GNRs superb dispersibility in common organic solvents, with a record concentration of ∼1 mg mL(-1) (for GNR backbone) that is much higher than that (<0.01 mg mL(-1)) of reported GNRs. Moreover, the PEO-functionalized GNRs can be readily dispersed in water, accompanying with supramolecular helical nanowire formation. Scanning probe microscopy reveals raft-like self-assembled monolayers of uniform GNRs on graphite substrates. Thin-film-based field-effect transistors (FETs) of the GNRs exhibit a high carrier mobility of ∼0.3 cm(2) V(-1) s(-1), manifesting promising application of the polymer-functionalized GNRs in electronic devices.

"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.

Graphene Meets Ionic Liquids: Fermi Level Engineering via Electrostatic Forces.

Graphene-based two-dimensional (2D) materials are promising candidates for a number of different energy applications. A particularly interesting one is in next generation supercapacitors, where graphene is being explored as an electrode material in combination with room temperature ionic liquids (ILs) as electrolytes. Because the amount of energy that can be stored in such supercapacitors critically depends on the electrode-electrolyte interface, there is considerable interest in understanding the structure and properties of the graphene/IL interface. Here, we report the changes in the properties of graphene upon adsorption of a homologous series of alkyl imidazolium tetrafluoroborate ILs using a combination of experimental and theoretical tools. Raman spectroscopy reveals that these ILs cause n-type doping of graphene, and the magnitude of doping increases with increasing cation chain length despite the expected decrease in the density of surface-adsorbed ions. Molecular modeling simulations show that doping originates from the changes in the electrostatic potential at the graphene/IL interface. The findings described here represent an important step in developing a comprehensive understanding of the graphene/IL interface.

Halogenated building blocks for 2D crystal engineering on solid surfaces: lessons from hydrogen bonding.

Halogen bonding has emerged as a promising tool in two-dimensional (2D) crystal engineering. Since halogen bonds are similar to hydrogen bonds in a number of aspects, the existing knowledge of hydrogen bonded systems can be applied to halogenated systems. Here we evaluate the applicability of a retrosynthetic approach based on topological similarity between hydrogen and halogen bonds to obtain predictable halogen bonded networks. The self-assembly of 1,3-dibromo-5-alkoxybenzene derivatives was studied in analogy with well-explored alkoxy isophthalic acids using a combination of experimental and theoretical tools. Scanning tunneling microscopy (STM) characterization of the networks formed at the liquid-graphite interface revealed that while the retrosynthetic approach works at the level of small clusters of molecules within the 2D network, the overall structure of the network deviates from the anticipated structure. The monolayers consist of fractured rows of halogen-bonded modules instead of the expected continuous lamellar structure. Each module consists of a discrete number of halogen-bonded molecules. The interactions responsible for the stabilization of halogen bonded dimers are delineated through detailed density functional theory (DFT) calculations coupled with natural bonding orbitals (NBO) and perturbation analysis. A modified force field that includes an extra charged site to imitate the σ hole on the halogen atom was developed and applied to extract total potential energies of the anticipated and observed networks. Plausible reasons for the deviation from the anticipated structure are discussed. Finally, a modified molecular design that allows successful application of the hydrogen bond-halogen bond analogy was tested experimentally.

Nanoscale Control over the Mixing Behavior of Surface-Confined Bicomponent Supramolecular Networks Using an Oriented External Electric Field.

Strong electric fields are known to influence the properties of molecules as well as materials. Here we show that by changing the orientation of an externally applied electric field, one can locally control the mixing behavior of two molecules physisorbed on a solid surface. Whether the starting two-component network evolves into an ordered two-dimensional (2D) cocrystal, yields an amorphous network where the two components phase separate, or shows preferential adsorption of only one component depends on the solution stoichiometry. The experiments are carried out by changing the orientation of the strong electric field that exists between the tip of a scanning tunneling microscope and a solid substrate. The structure of the two-component network typically changes from open porous at negative substrate bias to relatively compact when the polarity of the applied bias is reversed. The electric-field-induced mixing behavior is reversible, and the supramolecular system exhibits excellent stability and good response efficiency. When molecular guests are adsorbed in the porous networks, the field-induced switching behavior was found to be completely different. Plausible reasons behind the field-induced mixing behavior are discussed.

On the formation of concentric 2D multicomponent assemblies at the solution-solid interface.

We report on the design and fabrication of a four-component supramolecular network using the 'core-shell' approach. Each 'core' component templates the formation of an outer 'shell' leading to formation of three concentric 'shells' around the central guest. The 'shells' are formed only in presence of guests thus demonstrating remarkable selectivity in molecular recognition.

Reversible Local and Global Switching in Multicomponent Supramolecular Networks: Controlled Guest Release and Capture at the Solution/Solid Interface.

Dynamically switchable supramolecular systems offer exciting possibilities in building smart surfaces, the structure and thus the function of which can be controlled by using external stimuli. Here we demonstrate an elegant approach where the guest binding ability of a supramolecular surface can be controlled by inducing structural transitions in it. A physisorbed self-assembled network of a simple hydrogen bonding building block is used as a switching platform. We illustrate that the reversible transition between porous and nonporous networks can be accomplished using an electric field or applying a thermal stimulus. These transitions are used to achieve controlled guest release or capture at the solution-solid interface. The electric field and the temperature-mediated methods of guest release are operative at different length scales. While the former triggers the transition and thus guest release at the nanometer scale, the latter is effective over a much larger scale. The flexibility associated with physisorbed self-assembled networks renders this approach an attractive alternative to conventional switchable systems.