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.

Tunable doping of graphene by using physisorbed self-assembled networks.

One current key challenge in graphene research is to tune its charge carrier concentration, i.e., p- and n-type doping of graphene. An attractive approach in this respect is offered by controlled doping via well-ordered self-assembled networks physisorbed on the graphene surface. We report on tunable n-type doping of graphene using self-assembled networks of alkyl-amines that have varying chain lengths. The doping magnitude is modulated by controlling the density of the strong n-type doping amine groups on the surface. As revealed by scanning tunneling and atomic force microscopy, this density is governed by the length of the alkyl chain which acts as a spacer within the self-assembled network. The modulation of the doping magnitude depending on the chain length was demonstrated using Raman spectroscopy and electrical measurements on graphene field effect devices. This supramolecular functionalization approach offers new possibilities for controlling the properties of graphene and other two-dimensional materials at the nanoscale.

Insights into dynamic covalent chemistry at surfaces.

The potential of surface confined self-assembly to influence the chemical equilibrium of Schiff base formation and bias the yield and distribution of reaction products is explored.

Alkoxylated dehydrobenzo[12]annulene on Au(111): from single molecules to quantum dot molecular networks.

We demonstrate the effective confinement of surface electrons in the pores of molecular networks formed by dehydrobenzo[12]annulene (DBA) molecules with butoxy groups (DBA-OC4) on Au(111). Investigation of the network formation starting from single molecules reveals a considerable interaction of the molecules with the substrate, which is at the origin of the observed confinement.

On the stability of surface-confined nanoporous molecular networks.

Self-assembly of molecular building blocks into two-dimensional nanoporous networks has been a topic of broad interest for many years. However, various factors govern the specific outcome of the self-assembly process, and understanding and controlling these are key to successful creation. In this work, the self-assembly of two alkylated dehydrobenzo[12]annulene building blocks was compared at the liquid-solid interface. It turned out that only a small chemical modification within the building blocks resulted in enhanced domain sizes and stability of the porous packing relative to the dense linear packing. Applying a thermodynamic model for phase transition revealed some key aspects for network formation.

Efficient screening of 2D molecular polymorphs at the solution-solid interface.

Formation of multiple polymorphs during two-dimensional (2D) crystallization of organic molecules is more of a routine occurrence than rarity. Although such diverse crystalline structures provide exciting possibilities for studying crystal engineering in 2D, predicting the occurrence of polymorphs for a given building block is often non-trivial. Moreover, there is scarcity of methods that can experimentally verify the presence of such crystalline polymorphs in a straightforward fashion. Here we demonstrate a relatively simple experimental approach for screening of 2D polymorphs formed at the solution-solid interface. The strategy involves use of solution flow produced by contacting a piece of tissue paper to the sample to generate a lateral density gradient along the substrate surface. In situ generation of such gradient allows rapid discovery and nanoscale separation of multiple 2D polymorphs in a single experiment. The concept is demonstrated using three structurally different building blocks that differ in terms of intermolecular interactions responsible for 2D crystal formation. The method described here represents a powerful tool for efficient screening of 2D polymorphs formed at the solution-solid interface.

Nanostructuring graphene for controlled and reproducible functionalization.

The 'graphene rush' that started almost a decade ago is far from over. The dazzling properties of graphene have long warranted a number of applications in various domains of science and technology. Harnessing the exceptional properties of graphene for practical applications however has proved to be a massive task. Apart from the challenges associated with the large-scale production of the material, the intrinsic zero band gap, the inherently low reactivity and solubility of pristine graphene preclude its use in several high- as well as low-end applications. One of the potential solutions to these problems is the surface functionalization of graphene using organic building blocks. The 'surface-only' nature of graphene allows the manipulation of its properties not only by covalent chemical modification but also via non-covalent interactions with organic molecules. Significant amount of research efforts have been directed towards the development of functionalization protocols for modifying the structural, electronic, and chemical properties of graphene. This feature article provides a glimpse of recent progress in the molecular functionalization of surface supported graphene using non-covalent as well as covalent chemistry.

Self-assembly behavior of alkylated isophthalic acids revisited: concentration in control and guest-induced phase transformation.

The engineering of two-dimensional crystals by physisorption-based molecular self-assembly at the liquid-solid interface is a powerful method to functionalize and nanostructure surfaces. The formation of high-symmetry networks from low-symmetry building blocks is a particularly important target. Alkylated isophthalic acid (ISA) derivatives are early test systems, and it was demonstrated that to produce a so-called porous hexagonal packing of plane group p6, i.e., a regular array of nanowells, either short alkyl chains or the introduction of bulky groups within the chains were mandatory. After all, the van der Waals interactions between adjacent alkyl chains or alkyl chains and the surface would dominate the ideal hydrogen bonding between the carboxyl groups, and therefore, a close-packed lamella structure (plane group p2) was uniquely observed. In this contribution, we show two versatile approaches to circumvent this problem, which are based on well-known principles: the "concentration in control" and the "guest-induced transformation" methods. The successful application of these methods makes ISA suitable building blocks to engineer a porous pattern, in which the distance between the pores can be tuned with nanometer precision.

Tip-induced chemical manipulation of metal porphyrins at a liquid/solid interface.

Changing abruptly the potential between a scanning tunneling microscope tip and a graphite substrate induces "high-conductance" spots at the molecular level in a monolayer formed by a manganese chloride-porphyrin molecule. These events are attributed to the pulse-induced formation of µ-oxo-porphyrin dimers. The pulse voltage must pass a certain threshold for dimer formation, and pulse polarity determines the yield.

A single-molecule-level mechanistic study of Pd-catalyzed and Cu-catalyzed homocoupling of aryl bromide on an Au(111) surface.

On-surface Pd- and Cu-catalyzed C-C coupling reactions between phenyl bromide functionalized porphyrin derivatives on an Au(111) surface have been investigated under ultra-high vacuum conditions by using scanning tunneling microscopy and kinetic Monte Carlo simulations. We monitored the isothermal reaction kinetics by allowing the reaction to proceed at different temperatures. We discovered that the reactions catalyzed by Pd or Cu can be described as a two-phase process that involves an initial activation followed by C-C bond formation. However, the distinctive reaction kinetics and the C-C bond-formation yield associated with the two catalysts account for the different reaction mechanisms: the initial activation phase is the rate-limiting step for the Cu-catalyzed reaction at all temperatures tested, whereas the later phase of C-C formation is the rate-limiting step for the Pd-catalyzed reaction at high temperature. Analysis of rate constants of the Pd-catalyzed reactions allowed us to determine its activation energy as (0.41±0.03) eV.

Harnessing by a diacetylene unit: a molecular design for porous two-dimensional network formation at the liquid/solid interface.

Through the precise molecular design for alkoxy dehydro[12]annulene derivatives harnessed by a diacetylene unit in each alkyl chain, porous two-dimensional networks with giant pores were formed at the liquid/graphite interface.

Self-assembled air-stable supramolecular porous networks on graphene.

Functionalization and modification of graphene at the nanometer scale is desirable for many applications. Supramolecular assembly offers an attractive approach in this regard, as many organic molecules form well-defined patterns on surfaces such as graphite via physisorption. Here we show that ordered porous supramolecular networks with different pore sizes can be readily fabricated on different graphene substrates via self-assembly of dehydrobenzo[12]annulene (DBA) derivatives at the interface between graphene and an organic liquid. Molecular resolution scanning tunneling microscopy (STM) and atomic force microscopy (AFM) investigations reveal that the extended honeycomb networks are highly flexible and that they follow the topological features of the graphene surface without any discontinuity, irrespective of the step-edges present in the substrate underneath. We also demonstrate the stability of these networks under liquid as well as ambient air conditions. The robust yet flexible DBA network adsorbed on graphene surface is a unique platform for further functionalization and modification of graphene. Identical network formation irrespective of the substrate supporting the graphene layer and the level of surface roughness illustrates the versatility of these building blocks.

Temperature-induced structural phase transitions in a two-dimensional self-assembled network.

Two-dimensional (2D) supramolecular self-assembly at liquid-solid interfaces is a thermodynamically complex process producing a variety of structures. The formation of multiple network morphologies from the same molecular building blocks is a common occurrence. We use scanning tunnelling microscopy (STM) to investigate a structural phase transition between a densely packed and a porous phase of an alkylated dehydrobenzo[12]annulene (DBA) derivative physisorbed at a solvent-graphite interface. The influence of temperature and concentration are studied and the results combined using a thermodynamic model to measure enthalpy and entropy changes associated with the transition. These experimental results are compared to corresponding values obtained from simulations and theoretical calculations. This comparison highlights the importance of considering the solvent when modeling porous self-assembled networks. The results also demonstrate the power of using structural phase transitions to study the thermodynamics of these systems and will have implications for the development of predictive models for 2D self-assembly.

Coordination self-assembly of bromo-phenyl and pyridyl functionalized porphyrins with Fe on an Au(111) surface.

Using scanning tunneling microscopy, the coordination self-assembly of a series of peripheral bromo-phenyl and pyridyl substituted porphyrins with Fe was studied on an Au(111) surface. The porphyrins functionalized with two trans-pyridyl groups afford extended hexagonal frameworks and the porphyrins functionalized with three pyridyl groups generate discrete rosette and extended chiral kagome framework structures. The self-assembly of the porphyrin derivatives in which phenyl groups are substituted by bromo-phenyl results in coordination networks exhibiting identical structures to that of the parent compounds. These structures contain nanocavities decorated with Br, which provide potential for covalent functionalization.

Steering on-surface polymerization with metal-directed template.

On-surface polymerization represents a novel bottom-up approach for producing macromolecular structures. To date, however, most of the structures formed using this method exhibit a broad size distribution and are disorderly adsorbed on the surface. Here we demonstrate a strategy of using metal-directed template to control the on-surface polymerization process. We chose a bifunctional compound which contains pyridyl and bromine end groups as the precursor. Linear template afforded by pyridyl-Cu-pyridyl coordination effectively promoted Ullmann coupling of the monomers on a Au(111) surface. Taking advantage of efficient topochemical enhancement owing to the conformation flexibility of the Cu-pyridyl bonds, macromolecular porphyrin structures that exhibit a narrow size distribution were synthesized. We used scanning tunneling microscopy and kinetic Monte Carlo simulation to gain insights into the metal-directed polymerization at the single molecule level. The results reveal that the polymerization process profited from the rich chemistry of Cu which catalyzed the C-C bond formation, controlled the size of the macromolecular products, and organized the macromolecules in a highly ordered manner on the surface.

Two-dimensional metallo-supramolecular polymerization: toward size-controlled multi-strand polymers.

Multi-strand metallo-supramolecular polymers are self-assembled by pyridyl-functionalized porphyrin derivatives on a Au(111) surface through pyridyl-Cu-pyridyl coordination. Single-molecule-resolved characterization by scanning tunneling microscopy reveals a novel chain-growth polymerization mechanism for multi-strand supramolecular polymers. Furthermore, by varying the growth temperature and adding specific molecular modulators, both the length and the width of the polymers can be controlled.

Role of substrate in directing the self-assembly of multicomponent supramolecular networks at the liquid-solid interface.

The self-assembly of multicomponent networks at the liquid-solid interface between Au(111) or highly oriented pyrolytic graphite (HOPG) and organic solvents was investigated using scanning tunneling microscopy. Alkoxylated dehydrobenzo[12]annulene (DBA) derivatives form hexagonal nanoporous networks, which trap either single molecules of coronene (COR) or small clusters of COR and isophthalic acid to form multicomponent networks. The pattern of interdigitation between alkyl chains from DBA molecules produces hexagonal pores that are either chiral or achiral. On Au(111) substrates multicomponent networks display an ordered superlattice arrangement of chiral and achiral pores. In comparison, similar networks on HOPG display only chiral pores. The unique superlattice structure observed on Au(111) is related to a lower energetic preference for chiral pores than on HOPG and increased diffusion barriers for guest molecules. The increased diffusion barriers for guests allow them to act as nucleation sites for the formation of achiral pores. Following the initial nucleation of an achiral pore, restrictions imposed by the accommodation of guests within the porous network mean that subsequent growth naturally leads to the formation of the superlattice structure.

Exploring the complexity of supramolecular interactions for patterning at the liquid-solid interface.

The use of self-assembly to fabricate surface-confined adsorbed layers (adlayers) from molecular components provides a simple means of producing complex functional surfaces. The molecular self-assembly process relies on supramolecular interactions sustained by noncovalent forces such as van der Waals, electrostatic, dipole-dipole, and hydrogen bonding interactions. Researchers have exploited these noncovalent bonding motifs to construct well-defined two-dimensional (2D) architectures at the liquid-solid interface. Despite myriad examples of 2D molecular assembly, most of these early findings were serendipitous because the intermolecular interactions involved in the process are often numerous, subtle, cooperative, and multifaceted. As a consequence, the ability to tailor supramolecular patterns has evolved slowly. Insight gained from various studies over the years has contributed significantly to the knowledge of supramolecular interactions, and the stage is now set to systematically engineer the 2D supramolecular networks in a "preprogrammed" fashion. The control over 2D self-assembly of molecules has many important implications. Through appropriate manipulation of supramolecular interactions, one can "encode" the information at the molecular level via structural features such as functional groups, substitution patterns, and chiral centers which could then be retrieved, transferred, or amplified at the supramolecular level through well-defined molecular recognition processes. This ability allows for precise control over the nanoscale structure and function of patterned surfaces. A clearer understanding and effective use of these interactions could lead to the development of functional surfaces with potential applications in molecular electronics, chiral separations, sensors based on host-guest systems, and thin film materials for lubrication. In this Account, we portray our various attempts to achieve rational design of self-assembled adlayers by exploiting the aforementioned complex interactions at the liquid-solid interface. The liquid-solid interface presents a unique medium to construct flawless networks of surface confined molecules. The presence of substrate and solvent provides an additional handle for steering the self-assembly of molecules. Scanning tunneling microscopy (STM) was used for probing these molecular layers, a technique that serves not only as a visualization tool but could also be employed for active manipulation of molecules. The supramolecular systems described here are only weakly adsorbed on a substrate, which is typically highly oriented pyrolytic graphite (HOPG). Starting with fundamental studies of substrate and solvent influence on molecular self-assembly, this Account describes progressively complex aspects such as multicomponent self-assembly via 2D crystal engineering, emergence, and induction of chirality and stimulus responsive supramolecular systems.

One building block, two different nanoporous self-assembled monolayers: a combined STM and Monte Carlo study.

With the use of a single building block, two nanoporous patterns with nearly equal packing density can be formed upon self-assembly at a liquid-solid interface. Moreover, the formation of both of these porous networks can be selectively and homogenously induced by changing external parameters like solvent, concentration, and temperature. Finally, their porous properties are exploited to host up to three different guest molecules in a spatially resolved way.