Kunal S. Mali

Structurally Defined Graphene Nanoribbons with High Lateral Extension

Oxidative cyclodehydrogenation of laterally extended polyphenylene precursor allowed bottom-up synthesis of structurally defined graphene nanoribbons (GNRs) with unprecedented width. The efficiency of the cyclodehydrogenation was validated by means of MALDI-TOF MS, FT-IR, Raman, and UV-vis absorption spectroscopies as well as investigation of a representative model system. The produced GNRs demonstrated broad absorption extended to near-infrared region with the optical band gap of as low as 1.12 eV.

Bottom-Up Synthesis of Liquid-Phase-Processable Graphene Nanoribbons with Near-Infrared Absorption

Structurally defined, long (>100 nm), and low-band-gap (∼1.2 eV) graphene nanoribbons (GNRs) were synthesized through a bottom-up approach, enabling GNRs with a broad absorption spanning into the near-infrared (NIR) region. The chemical identity of GNRs was validated by IR, Raman, solid-state NMR, and UV-vis-NIR absorption spectroscopy. Atomic force microscopy revealed well-ordered self-assembled monolayers of uniform GNRs on a graphite surface upon deposition from the liquid phase. The broad absorption of the low-band-gap GNRs enables their detailed characterization by Raman and time-resolved terahertz photoconductivity spectroscopy with excitation at multiple wavelengths, including the NIR region, which provides further insights into the fundamental physical properties of such graphene nanostructures.

Hydrogen Bonding Versus van der Waals Interactions: Competitive Influence of Noncovalent Interactions on 2D Self‐Assembly at the Liquid–Solid Interface

The structures of the self-assembled monolayers of various 4-alkoxybenzoic acids physisorbed at the liquid-solid interface were established by employing scanning tunnelling microscopy (STM). This study has been essentially undertaken to explore the competitive influence of van der Waals and hydrogen-bonding interactions on the process of two-dimensional self-assembly. These acid derivatives form hydrogen-bonded dimers as expected; however, the dimers organise themselves in the form of relatively complex lamellae. The characteristic feature of these lamellae is the presence of regular discommensurations or kinks along the lamella propagation direction. The formation of kinked lamellae is discussed in light of the registry mechanism of the alkyl chains with the underlying graphite substrate. The location of the kinks along a lamella depends on the number (odd or even) of carbon atoms in the alkyl chain. This result indicates that concerted van der Waals interactions of the alkyl chain units introduce the odd/even chain-length effect on the surface-assembled supramolecular patterns. The odd/even effects are retained even upon complexation with a hydrogen-bond acceptor. However, as the solvent is changed from 1-phenyloctane to 1-octanoic acid, the kinked lamellae as well as the odd/even effects disappear. This solvent-induced convergence of supramolecular patterns is attained by means of co-crystallisation of octanoic acid molecules in the 2D crystal lattice, which is evident from high-resolution STM images. The solvent co-adsorption phenomenon is discussed in terms of competing van der Waals and hydrogen-bonding interactions.

Solvent-Induced Homochirality in Surface-Confined Low-Density Nanoporous Molecular Networks

Induction of chirality in achiral monolayers has garnered considerable attention in the recent past not only due to its importance in chiral resolutions and enantioselective heterogeneous catalysis but also because of its relevance to the origin of homochirality in life. In this contribution, we demonstrate the emergence of macroscopic chirality in multicomponent supramolecular networks formed by achiral molecules at the interface of a chiral solvent and an achiral substrate. The solvent-mediated chiral induction provides a simple, efficient, and versatile approach for the fabrication of homochiral surfaces using achiral building blocks.

Host–guest chemistry in two-dimensional supramolecular networks

Nanoporous supramolecular networks physisorbed on solid surfaces have been extensively used to immobilize a variety of guest molecules. Host-guest chemistry in such two-dimensional (2D) porous networks is a rapidly expanding field due to potential applications in separation technology, catalysis and nanoscale patterning. Diverse structural topologies with high crystallinity have been obtained to capture molecular guests of different sizes and shapes. A range of non-covalent forces such as hydrogen bonds, van der Waals interactions, coordinate bonds have been employed to assemble the host networks. Recent years have witnessed a surge in the activity in this field with the implementation of rational design strategies for realizing controlled and selective guest capture. In this feature article, we review the development in the field of surface-supported host-guest chemistry as studied by scanning tunneling microscopy (STM). Typical host-guest architectures studied on solid surfaces, both under ambient conditions at the solution-solid interface as well as those formed at the ultrahigh vacuum (UHV)-solid interface, are described. We focus on isoreticular host networks, hosts functionalized pores and dynamic host-guest systems that respond to external stimuli.

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.

Dynamic control over supramolecular handedness by selecting chiral induction pathways at the solution–solid interface

A dominant theme within the research on two-dimensional chirality is the sergeant-soldiers principle, wherein a small fraction of chiral molecules (sergeants) is used to skew the handedness of achiral molecules (soldiers) to generate a homochiral surface. Here, we have combined the sergeant-soldiers principle with temperature-dependent molecular self-assembly to unravel a peculiar chiral amplification mechanism at the solution-solid interface in which, depending on the concentration of a sergeant-soldiers solution, the majority handedness of the system can either be amplified or entirely reversed after an annealing step, furnishing a homochiral surface. Two discrete pathways that affect different stages of two-dimensional crystal growth are invoked for rationalizing this phenomenon and we present a set of experiments where the access to each pathway can be precisely controlled. These results demonstrate that a detailed understanding of subtle intermolecular and interfacial interactions can be used to induce drastic changes in the handedness of a supramolecular network.

Processable Rylene Diimide Dyes up to 4nm 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.

Scanning Tunneling Microscopy-Induced Reversible Phase Transformation in the Two-Dimensional Crystal of a Positively Charged Discotic Polycyclic Aromatic Hydrocarbon

We report on the observation and manipulation of a two-dimensional crystal formed by a positively charged discotic polycyclic aromatic hydrocarbon at the liquid-solid interface. Using scanning tunneling microscopy (STM) as a tool, the supramolecular scaffolds of charged molecules could be switched between dissimilar polymorphs of different molecular densities. The observed phase transformation was found to be driven by electrical parameters such as magnitude of change of the substrate bias and voltage pulses applied to the STM tip. We conclude that the electrical manipulation of these charged molecules is a result of the creation of large local electric fields that interact with the adsorbed ionic molecules and thus cause molecular rearrangement.

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.