Molecular islands at the liquid-solid interface.

Molecular islands of various shapes and sizes composed of a few tens of molecules only are formed at the liquid-solid interface, at room temperature, by an alkoxylated dehydrobenzo[12]annulene (DBA) derivative. Molecules are packed into hexagons. Scanning tunneling microscopy reveals the variety in molecular island structures and their stability.

Chiral Solvent-Induced Homochiral Hierarchical Molecular Assemblies at the Liquid/Solid Interface.

We herein investigate the formation of homochiral hierarchical self-assembled molecular networks (SAMNs) via chirality induction by the coadsorption of a chiral solvent at the liquid/graphite interface by means of scanning tunneling microscopy (STM). In a mixture of achiral solvents, 1-hexanoic acid, and 1,2,4-trichlorobenzene, an achiral dehydrobenzo[12]annulene (DBA) derivative with three alkoxy and three hydroxy groups in an alternating manner forms chiral hierarchical triangular cluster structures through dynamic self-sorting. Enantiomorphous domains appear in equal probability.

Adsorption of Prochiral Solvent Molecules by Surface-Confined Chiral Supramolecular Assemblies: How Solvent Impacts on-Surface Chirality.

The understanding of supramolecular chirality in self-assembled molecular networks (SAMNs) on surfaces generates a lot of interest because of its relation to the production of chiral sensors, reactors, and catalysts. We herein report the adsorption of a prochiral solvent molecule in porous SAMNs formed by a chiral dehydrobenzo[12]annulene (cDBA) derivative. Through the prochirality recognition of a solvent molecule, the supramolecular chirality of the SAMN is switched: the cDBA exclusively forms a counter-clockwise pore through co-adsorption of the solvent molecule in prochiral 1,2,4-trichlorobenzene, while in 1-phenyloctane it produces the opposite chiral, clockwise pore.

Synthesis and Reactivity of an X-Shaped Molecule: Reversible Formation and Cleavage of a Four-Membered Ring in Response to External Stimuli.

We herein report the synthesis and reactivity of an X-shaped molecule featuring three four-membered rings (4MRs) arranged in a ladder configuration. This molecule exhibits a reversible opening and closure of the central 4MR upon exposure to light irradiation and thermal treatment. The central 4MR of this molecule is also cleaved via electrochemical and chemical reductions.

Heptagonal Molecular Tiling via Self-Assembly of Heptagonal Phenylene-Ethynylene Macrocycle at the Liquid-Solid Interface.

The molecular-level scrutinization of on-surface tiling garners considerable interest among scientists. Herein, we demonstrate molecular-level heptagonal tiling using the self-assembly of a heptagonal meta-phenylene-ethynylene macrocycle featuring 14 long alkoxy substituents at the liquid-graphite interface using scanning tunneling microscopy. This heptagonal macrocycle produces an antiparallel pattern at the 1-phenyloctane-graphite interface through van der Waals interactions between the alkoxy chains.

Homochiral hierarchical molecular assemblies through dynamic combination of conformational states of a single chiral building block at the liquid/solid interface.

We herein report the construction of homochiral, hierarchical self-assembled molecular networks (SAMNs) at the liquid/graphite interface using a single molecular building block, a chiral dehydrobenzo[12]annulene (cDBA) derivative with three chiral alkoxy and three hydroxy groups positioned in an alternating manner on the DBA core. The cDBA molecules form homochiral hierarchical SAMNs consisting of triangular clusters of several sizes, the size of which can be tuned by solvent polarity and solute concentration, reaching periodicities as large as 9.3 nm.

Formation of Supramolecular Heterostacks at the Liquid-Solid Interface: Impact of Symmetry Mismatching on Structural Growth.

The construction of intricate three-dimensional (3D) nanoarchitectures on surfaces through molecular self-assembly attracts attention not only from a crystal engineering viewpoint but also because of its potential in a range of applications, given the current interest in van der Waals heterostructures. We herein report the formation of porous structures on alkane buffer layers on graphite. A dehydrobenzo[12]annulene (DBA) derivative having six decyloxy chains forms hexagonal structures on -pentacontane and -hexacontane buffer layers through van der Waals interactions at the 1-octanoic acid/graphite interface.

On the role of functional groups in the formation of diazonium based covalent attachments: dendritic layer-by-layer growth.

Multilayered growth is often observed upon electrografting aryl diazonium derivatives on graphitic substrates due to the reactive nature of aryl radicals. The mechanism of the multilayer formation has been investigated either by measuring the thickness of the grafted layer, the charge transfer, or simulations. Spectroscopy and in particular microscopy approaches are underrepresented.

Nanoscale chemical patterning of graphite at different length scales.

Chemical patterning surfaces is relevant in several different domains of science and technology with exciting possibilities in electronics, catalysis, sensing, and photonics. Here, we present a novel strategy for chemical patterning of graphite using a combination of covalent and non-covalent approaches. Building on our previous work, where self-assembled monolayers of linear alkanes were used as sacrificial masks for directing the covalent anchoring of aryl groups to the graphite surface in sub-10 nm arrays, we present a modified design of a template alkane with alkoxy terminal groups which allowed better pattern transfer fidelity in comparison to simple linear alkanes.

Spatially Controlled Aryl Radical Grafting of Graphite Surfaces Guided by Self-Assembled Molecular Networks of Linear Alkane Derivatives: The Importance of Conformational Dynamics.

The covalent functionalization of carbon surfaces with nanometer-scale precision is of interest because of its potential in a range of applications. We herein report the controlled grafting of graphite surfaces using electrochemically generated aryl radicals templated by self-assembled molecular networks (SAMNs) of bisalkylurea derivatives. A bisalkylurea derivative having two butoxy units acts as a template for the covalent functionalization of aryl groups in between self-assembled rows of this molecule.

Linear π-conjugated polycyclic compounds consisting of four-, five-, and six-membered rings: benzo[1'',2'':3,4;4'',5'':3',4']bis(cyclobuta[1,2-]thiophene).

Linear π-conjugated polycyclic compounds, BBCTs, containing linearly annulated 5-, 4-, 6-, 4-, and 5-membered rings were produced copper-mediated double intramolecular coupling reactions. The absorption spectra and electrochemical results confirmed their moderate optical energy gaps and high HOMO energy levels, respectively. In a crystalline state, the BBCT molecules adopt a herringbone structure, while the methylated molecules form slipped one-dimensional columns.

Spontaneous and scanning-assisted desorption-adsorption dynamics in porous supramolecular networks at the solution-solid interface.

Self-assembled molecular networks (SAMNs) are formed by the spontaneous assembly of molecules on surfaces. On conductive atomically flat surfaces, and also at the liquid-solid interface, scanning tunneling microscopy (STM) can follow their growth dynamics. Desorption and adsorption dynamics are difficult to probe through the liquid-solid interface.

Solvent Mediated Nanoscale Quasi-Periodic Chirality Reversal in Self-Assembled Molecular Networks Featuring Mirror Twin Boundaries.

Grain boundaries in polycrystals have a prominent impact on the properties of a material, therefore stimulating the research on grain boundary engineering. Structure determination of grain boundaries of molecule-based polycrystals with submolecular resolution remains elusive. Reducing the complexity to monolayers has the potential to simplify grain boundary engineering and may offer real-space imaging with submolecular resolution using scanning tunneling microscopy (STM).

Symmetry and spacing controls in periodic covalent functionalization of graphite surfaces templated by self-assembled molecular networks.

We herein present the periodic covalent functionalization of graphite surfaces, creating a range of patterns of different symmetries and pitches at the nanoscale. Self-assembled molecular networks (SAMNs) of rhombic-shaped bis(dehydrobenzo[12]annulene) (bisDBA) derivatives having alkyl chain substituents of different lengths were used as templates for covalent grafting of electrochemically generated aryl radicals. Scanning tunneling microscopy (STM) observations at the 1,2,4-trichlorobenzene/graphite interface revealed that these molecules form a variety of networks that contain pores of different shapes and sizes.

Revisiting Dehydrothiopheno[12]annulenes: Synthesis, Electronic Properties, and Aromaticity.

The aromaticity and electronic properties of acetylene-bridged hexadehydrotristhiopheno[12]annulenes (s) were revisited using a combined experimental and theoretical approach. Moreover, we attempted the synthesis of the butadiyne-bridged octadehydrobisthiopheno[12]annulenes (s). While the formation of s was indicated by NMR spectroscopy, mass spectrometry, and UV-vis absorption measurements, our attempts to isolate s were unsuccessful on account of its instability.

Hierarchical two-dimensional molecular assembly through dynamic combination of conformational states at the liquid/solid interface.

Self-sorting of multiple building blocks for correctly positioning molecules through orthogonal recognition is a promising strategy for construction of a hierarchical self-assembled molecular network (SAMN) on a surface. Herein we report that a trigonal molecule, dehydrobenzo[12]annulene (DBA) derivative having three tetradecyloxy chains and three hydroxy groups in an alternating manner, forms hierarchical triangular clusters of different sizes ranging from 2.4 to 16.

Chirality in porous self-assembled monolayer networks at liquid/solid interfaces: induction, reversion, recognition and transfer.

Chirality in two dimensions (2D) has attracted increasing attention with regard to interesting fundamental aspects as well as potential applications. This article reports several aspects of supramolecular chirality control as exemplified by self-assembled monolayer networks (SAMNs) formed by a class of chiral building blocks consisting of a triangular conjugated core and alkoxy chains on the periphery. It highlights 2D chirality induction phenomena through a classic "sergeants-and-soldiers" mechanism, in which the inducer is incorporated into a network component, as well as through a "supramolecular host-guest" mechanism, in which the inducer is entrapped in the porous space, leading to counterintuitive chirality reversal.

Stereospecific Epitaxial Growth of Bilayered Porous Molecular Networks.

Stereocontrolled multilayer growth of supramolecular porous networks at the interface between graphite and a solution was investigated. For this study, we designed a chiral dehydrobenzo[12]annulene (DBA) building block bearing alkoxy chains substituted at the 2 position with hydroxy groups, which enable van der Waals stabilization in a layer and potential hydrogen-bonding interactions between the layers. Bias voltage-dependent scanning tunneling microscopy (STM) experiments revealed the diastereospecificity of the bilayer with respect to both the intrinsic chirality of the building blocks and the supramolecular chirality of the self-assembled networks.

Trapping a pentagonal molecule in a self-assembled molecular network: an alkoxylated isosceles triangular molecule does the job.

We herein report a unique example of on-surface adaptive self-assembly. A pentagon-shaped macrocycle, cyclic [5]meta-phenyleneacetylene [5]CMPA, is trapped by the adaptive supramolecular network formed by an isosceles triangular molecule, alkoxy substituted dehydrobenzo[14]annulene [14]ISODBA at the liquid/graphite interface, leading to a highly ordered and large-area bicomponent self-assembled molecular network (SAMN), as revealed by scanning tunneling microscopy (STM).

Porous Self-Assembled Molecular Networks as Templates for Chiral-Position-Controlled Chemical Functionalization of Graphitic Surfaces.

Controlled covalent functionalization of graphitic surfaces with molecular scale precision is crucial for tailored modulation of the chemical and physical properties of carbon materials. We herein present that porous self-assembled molecular networks (SAMNs) act as nanometer scale template for the covalent electrochemical functionalization of graphite using an aryldiazonium salt. Hexagonally aligned achiral grafted species with lateral periodicity of 2.

Electrostatically Driven Guest Binding in Self-Assembled Molecular Network of Hexagonal Pyridine Macrocycle at the Liquid/Solid Interface: Symmetry Breaking Induced by Coadsorbed Solvent Molecules.

We present here the construction of a self-assembled two-dimensional network at the liquid/solid interface using a hexagonal pyridine macrocycle which binds an organic cation in its intrinsic porous space by electrostatic interactions. For this purpose, a hexagonal pyridinylene-butadiynylene macrocycle (PyBM) having six octyloxymethyl groups, , was synthesized. As guests, tropylium () tetrafluoroborate and trioxatriangulenium () hexafluorophosphate were used.

Theoretical Study on the Geometry, Aromaticity, and Electronic Properties of Benzo[3,4]cyclobutathiophenes and Their Homologues.

The geometry, aromaticity, and electronic properties of benzo[3,4]cyclobutathiophenes (BCTs) and their homologues have been examined theoretically using density functional theory calculations. The harmonic oscillator measure of aromaticity and nucleus-independent chemical shift analyses revealed the aromaticity characteristics of the two regioisomers benzo[3,4]cyclobuta[1,2-]thiophene and benzo[3,4]cyclobuta[1,2-]thiophene. When the aromaticity of one of the six-π-electron rings increases, it concomitantly decreases in the other ring.

On-Surface Evolution of meso-Isomerism in Two-Dimensional Supramolecular Assemblies.

Chiral structures created through the adsorption of molecules onto achiral surfaces play pivotal roles in many fields of science and engineering. Here, we present a systematic study of a novel chiral phenomenon on a surface in terms of organizational chirality, that is, meso-isomerism, through coverage-driven hierarchical polymorphic transitions of supramolecular assemblies of highly symmetric π-conjugated molecules. Four coverage-dependent phases of dehydrobenzo[12]annulene were uniformly fabricated on Ag(111), exhibiting unique chiral characteristics from the single-molecule level to two-dimensional supramolecular assemblies.

Reversing the Handedness of Self-Assembled Porous Molecular Networks through the Number of Identical Chiral Centres.

Scanning tunnelling microscope observations at the 1-phenyloctane/graphite interface reveal how chiral structural information at the molecular level is transferred and expressed structurally at the 2D supramolecular level for a porous system. The chirality of self-assembled molecular networks formed by chiral dehydrobenzo[12]annulene (cDBA) derivatives having three chiral chains and three achiral chains, alternatingly, is compared with those of cDBAs having six chiral chains reported previously. While for all cDBAs homochiral surfaces are formed, their handedness is not simply a reflection of the absolute configuration of the stereogenic centres.