Halogen bonds in 2D supramolecular self-assembly of organic semiconductors

Weak interactions between bromine, sulphur, and hydrogen are shown to stabilize 2D supramolecular monolayers at the liquid–solid interface. Three different thiophene-based semiconducting organic molecules assemble into close-packed ultrathin ordered layers. A combination of scanning tunneling microscopy (STM) and density functional theory (DFT) elucidates the interactions within the monolayer. Electrostatic interactions are identified as the driving force for intermolecular Br⋯Br and Br⋯H bonding. We find that the S⋯S interactions of the 2D supramolecular layers correlate with the hole mobilities of thin film transistors of the same materials.

Chemical nano-gardens: growth of salt nanowires from supramolecular self-assembly gels.

In this article, we examine the phenomenon of single-crystal halide salt wire growth at the surface of porous materials. We report the use of a single-step casting technique with a supramolecular self-assembly gel matrix that upon drying leads to the growth of single-crystal halide (e.g., NaCl, KCl, and KI) nanowires with diameters ~130-200 nm. We demonstrate their formation using electron microscopy and electron-dispersive X-ray spectroscopy, showing that the supramolecular gel stabilizes the growth of these wires by facilitating a diffusion-driven base growth mechanism. Critically, we show that standard non-supramolecular gels are unable to facilitate nanowire growth. We further show that these nanowires can be grown by seeding, forming nanocrystal gardens. This study helps understand the possible prefunctionalization of membranes to stimulate ion-specific filters or salt efflorescence suppressors, while also providing a novel route to nanomaterial growth.

Self-assembly of a halogenated molecule on oxide-passivated Cu(110)

The supramolecular self-assembly of brominated molecules was investigated and compared on Cu(110) and Cu(110)[BOND]O(2×1) surfaces under ultrahigh vacuum. By using scanning tunnelling microscopy, we show that brominated molecules form a disordered structure on Cu(110), whereas a well-ordered supramolecular network is observed on the Cu(110)[BOND]O(2×1) surface. The different adsorption behaviors of these two surfaces are described in terms of weakened molecule–substrate interactions on Cu(110)[BOND]O(2×1) as opposed to bare Cu(110). The effect of oxygen-passivation is to suppress debromination and it can be a convenient approach for investigating other self-assembly processes on copper-based substrates.

From Molecular to Supramolecular: An Exploration into the Modes of Self-assembly in Conformationally Locked Polycyclitols

This brief account highlights the notable findings of our investigation into the supramolecular chemistry of conformationally locked polycyclitols in the solid state. The study was aimed at analyzing the crystal packing and unraveling the modalities of non-covalent interactions (particularly, intramolecular vis-a-vis intermolecular OH center dot center dot center dot O hydrogen bonds) in polyols. The know-how obtained thereof, was successfully utilized to engineer self-assemblies of designer polycyclitols, having hydrogen bond donors and acceptors fettered onto a trans-decalin scaffold. The results seek to draw particular attention to the intrinsic attribute of this rigid carbocyclic framework to lock functional groups into spatially invariant positions and bring potential intramolecular hydrogen bonding partners into favorable interaction geometry to engender predictability in the self-assembly patterns.

Europium-directed self-assembly of a luminescent supramolecular gel from a tripodal terpyridine-based ligand.

Eu(III), the last piece in the puzzle: Europium-induced self-assembly of ligands having a C(3)-symmetrical benzene-1,3,5-tricarboxamide core results in the formation of luminescent gels. Supramolecular polymers are formed through hydrogen bonding between the ligands. The polymers are then brought together into the gel assembly through the coordination of terpyridine ends by Eu(III) ions (blue dashed arrow: distance between two ligands in the strand direction).

Luminescent supramolecular microstructures containing Ru(bpy)(3)(2+): Solution-based self-assembly preparation and solid-state electrochemiluminescence detection application

In this correspondence, we report on the first preparation of novel, robust Ru(bpy)(3)(2+)-containing supramolecular microstructures via a solution-based self-assembly strategy, carried out by directly mixing H2PtCl6 and Ru(bpy)(3)Cl-2 aqueous solutions at room temperature. It reveals that both the molar ratio and concentration of reactants have a heavy influence on the morphologies of such microstructures. The electrochemical behavior of the Ru(bpy)(3)(2+) components contained in the solid film of the microstructures formed on the electrode surface is also studied and found to exhibit a diffusion-controlled voltammetric feature. Most importantly, such microstructures exhibit excellent electrochemiluminescence (ECL) behaviors and therefore hold great promise as new luminescent materials for solid-state ECL detection in capillary electrophoresis (CE) or CE microchip.

Nucleobase-metal hybrid materials: Preparation of submicrometer-scale, spherical colloidal particles of adenine-gold(III) via a supramolecular hierarchical self-assembly approach

We report a simple and effective supramolecular route for facile synthesis of submicrometer-scale, hierarchically self-assembled spherical colloidal particles of adenine - gold(III) hybrid materials at room temperature. Simple mixture of the precursor aqueous solutions of adenine and HAuCl4 at room temperature could result in spontaneous formation of the hybrid colloidal particles. Optimization of the experimental conditions could yield uniform-sized, self-assembled products at 1:4 molar ration of adenine to HAuCl4. Transmission electron microscopy results reveal the formation of hierarchical self-assembled structure of the as-prepared colloidal particles. Concentration dependence, ratio dependence, time dependence, and kinetic measurements have been investigated. Moreover, spectroscopic evidence [i.e., Fourier transform infrared (FTIR) and UV-vis spectra and wide-angle X-ray scattering data] of the interaction motives causing the formation of the colloidal particles is also presented.

Molecular tectonics : supramolecular 2D nanopatterning of surfaces by self-assembly

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal

Controlled Self-assembly of p-Phenyleneethynylene Derivatives to Diverse Supramolecular Architectures

Regional Research Laboratory

Stepwise self-assembly of a tripeptide from molecular dimers to supramolecular beta-sheets in crystals and amyloid-like fibrils in the solid state

The terminally protected tripeptide Boc-Ala(1)-Leu(2)-Ala(3)-OMe 1 forms antiparallel hydrogen-bonded dimers of two different conformers in the asymmetric unit and the individual dimers then self-associate to form supramolecular beta-sheet structures in crystals and amyloid-like fibrils in the solid state.

Supramolecular helix and beta-sheet through self-assembly of two isomeric tetrapeptides in crystals and formation of filaments and ribbons in the solid state

Single crystal X-ray diffraction studies show that the beta-turn structure of tetrapeptide I, Boc-Gly-Phe-Aib-Leu-OMe (Aib: alpha-amino isobutyric acid) self-assembles to a supramolecular helix through intermolecular hydrogen bonding along the crystallographic a axis. By contrast the beta-turn structure of an isomeric tetrapeptide II, Boc-Gly-Leu-Aib-Phe-OMe self-assembles to a supramolecular beta-sheet-like structure via a two-dimensional (a, b axis) intermolecular hydrogen bonding network and pi-pi interactions. FT-IR studies of the peptides revealed that both of them form intermolecularly hydrogen bonded supramolecular structures in the solid state. Field emission scanning electron micrographs (FE-SEM) of the dried fibrous materials of the peptides show different morphologies, non-twisted filaments in case of peptide I and non-twisted filaments and ribbon-like structures in case of peptide II.

Formation of a one-dimensional helical alignment of water molecules within a water-mediated supramolecular helix using molecular self-assembly of a water-soluble short pseudopeptide

The reported pseudopeptide 1 adopts a double turn molecular conformation consisting of an intramolecular 9-membered turn together with a water-mediated 11-atom turn and this pseudopeptide 1 self-assembles to form a water-mediated supramolecular helical structure with internal water molecules, which are aligned in a ID helical array. (c) 2006 Elsevier Ltd. All rights reserved.

Overlapping double turn conformations adopted by tetrapeptides containing non-coded alpha-Amino Isobutyric Acid (AIB) and formation of tape-like structures through supramolecular helix mediated self-assembly

Single crystal X-ray diffraction studies and solvent dependent H-1 NMR titrations reveal that a set of four tetrapeptides with general formula Boc-Xx(1)-Aib(2)-Yy(3)-Zz(4)-OMe, where Xx, Yy and Zz are coded L- amino acids, adopt equivalent conformations that can be described as overlapping double turn conformations stabilized by two 4 -> 1 intramolecular hydrogen bonds between Yy(3)-NH and Boc C=O and Zz(4)-NH and Xx(1)C=O. In the crystalline state, the double turn structures are packed in head-to-tail fashion through intermolecular hydrogen bonds to create supramolecular helical structures. Field emission scanning electron microscopic (FE-SEM) images of the tetrapeptides in the solid state reveal that they can form flat tape-like structures. The results establish that synthetic Aib containing supramolecular helices can form highly ordered self-aggregated amyloid plaque like human amylin.

Design of supramolecular beta-sheet forming beta-turns containing aromatic rings and non-coded alpha-aminoisobutyric acid and the formation of flat fibrillar structures through self-assembly

Single crystal X-ray diffraction studies show that the three designed tripeptides Boc-Leu-Aib-m-NA-NO2 (I), Boc-Phe-Aib-m-NA-NO2 (II) and Boc-Pro-Aib-m-ABA-OMe (III) (Aib, -aminoisobutyric acid; m-NA, m-nitroaniline; m-ABA, m-aminobenzoic acid; Boc, t-butyloxycarbonyl) containing aromatic rings in the backbones adopt -turn structures that are self-assembled through intermolecular hydrogen bonds and van der Waals interactions to create layers of -sheets. Solvent-dependent NMR titration and CD studies show that the -turn structures of the peptides also exist in the solution phase. The field emission scanning electron microscopic and transmission electron microscopic images of the peptides in the solid state reveal fibrillar structures of flat morphology that are formed through -sheet mediated self-assembly of the preorganised -turn building blocks.