Ambient Bistable Single Dipole Switching in a Molecular Monolayer

Reported here is a molecular dipole that self‐assembles into highly ordered patterns at the liquid‐solid interface, and it can be switched at room temperature between a bright and a dark state at the single‐molecule level. Using a scanning tunneling microscope (STM) under suitable bias conditions, binary information can be written at a density of up to 41 Tb cm−2 (256 Tb/in2). The written information is stable during reading at room temperature, but it can also be erased at will, instantly, by proper choice of tunneling conditions. DFT calculations indicate that the contrast and switching mechanism originate from the stacking sequence of the molecular dipole, which is reoriented by the electric field between the tip and substrate

Halogen Bonding in Two-Dimensional Crystal Engineering

Halogen bonds, which provide an intermolecular interaction with moderate strength and high directionality, have emerged as a promising tool in the repertoire of non-covalent interactions. In this review, we provide a survey of the literature where halogen bonding was used for the fabrication of supramolecular networks on solid surfaces. The definitions of, and the distinction between halogen bonding and halogen-halogen interactions are provided. Self-assembled networks formed at the solution/solid interface and at the vacuum-solid interface, stabilized in part by halogen bonding, are discussed. Besides the broad classification based on the interface at which the systems are studied, the systems are categorized further as those sustained by halogen-halogen and halogen-heteroatom contacts.status: publishe

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.crosscheck: This document is CrossCheck deposited copyright_licence: The Royal Society of Chemistry has an exclusive publication licence for this journal copyright_licence: This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0) history: Received 23 June 2016; Accepted 18 August 2016; Advance Article published 30 August 2016; Version of Record published 20 September 2016status: publishe

Frontiers of supramolecular chemistry at solid surfaces

Supramolecular chemistry on solid surfaces represents an exciting field of research that continues to develop in new and unexpected directions.</p

Manifestations of Non-Planar Adsorption Geometries of Lead Pyrenocyanine at the Liquid-Solid Interface

In this work, we provide evidence for multiple non-planar adsorption geometries of a novel pyrenocyanine derivative at the liquid-solid interface under ambient conditions. When adsorbed at the organic liquid-solid interface, lead pyrenocyanine forms well-ordered monolayers that exhibit peculiar non-periodic contrast variation. The different contrast of the adsorbed molecules is attributed to dissimilar adsorption geometries which arise from the non-planar conformation of the molecules. The non-planarity of the molecular backbone in turn arises due to a combination of the angularly extended pyrene subunits and the presence of the large lead ion, which is too big to fit inside the central cavity and thus is located out of the aromatic plane. The two possible locations of the lead atom, namely below and above the aromatic plane, could be identified as depression and protrusion in the central cavity, respectively. The manifestation of such multiple adsorption geometries on the structure of the resultant monolayer is discussed in detail. The packing density of these 2D arrays of molecules could be tuned by heating of the sample wherein the molecular packing changes from a low-density, pseudo six-fold symmetric to a high-density, two-fold symmetric arrangement. Finally, a well-ordered two-component system could be constructed by incorporating C60 molecules in the adlayer of lead pyrenocyanine at the liquid-solid interface.status: publishe

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.status: publishe

Complex Chiral Induction Processes at the Solution/Solid Interface

Two-dimensional supramolecular chirality is often achieved by confining molecules against a solid surface. The sergeants−soldiers principle is a popular strategy to fabricate chiral surfaces using predominantly achiral molecules. In this method, achiral molecules (the soldiers) are forced to assemble in a chiral fashion by mixing them with a small percentage of structurally similar chiral molecules (the sergeants). The full complexity of the amplification processes in chiral induction studies is rarely revealed due to the specific experimental conditions used. Here we report the evolution of chirality in mixed supramolecular networks of chiral and achiral dehydrobenzo[12]annulene (DBA) derivatives using scanning tunneling microscopy (STM) at the solution/solid interface. The experiments were carried out in the high sergeants−soldiers mole ratio regime in relatively concentrated solutions. Variation in the sergeants/soldiers composition at a constant solution concentration revealed different mole ratio regimes where either amplification of supramolecular handedness as defined by the sergeant chirality or its reversal was observed. The chiral induction/reversal processes were found to be a convolution of different phenomena occurring at the solution-solid interface namely, structural polymorphism, competitive adsorption and adaptive host−guest recognition. Grasping the full complexity of chiral amplification processes as described here is a stepping-stone toward developing a predictive understanding of chiral amplification processes.status: publishe

Complex Chiral Induction Processes at the Solution/Solid Interface

Two-dimensional supramolecular chirality is often achieved by confining molecules against a solid surface. The sergeants−soldiers principle is a popular strategy to fabricate chiral surfaces using predominantly achiral molecules. In this method, achiral molecules (the soldiers) are forced to assemble in a chiral fashion by mixing them with a small percentage of structurally similar chiral molecules (the sergeants). The full complexity of the amplification processes in chiral induction studies is rarely revealed due to the specific experimental conditions used. Here we report the evolution of chirality in mixed supramolecular networks of chiral and achiral dehydrobenzo[12]annulene (DBA) derivatives using scanning tunneling microscopy (STM) at the solution/solid interface. The experiments were carried out in the high sergeants−soldiers mole ratio regime in relatively concentrated solutions. Variation in the sergeants/soldiers composition at a constant solution concentration revealed different mole ratio regimes where either amplification of supramolecular handedness as defined by the sergeant chirality or its reversal was observed. The chiral induction/reversal processes were found to be a convolution of different phenomena occurring at the solution-solid interface namely, structural polymorphism, competitive adsorption and adaptive host−guest recognition. Grasping the full complexity of chiral amplification processes as described here is a stepping-stone toward developing a predictive understanding of chiral amplification processes.status: publishe