Search results for "Supramolecular"
showing 10 items of 830 documents
Noncovalent assembly of functional groups on calix[4]arene molecular boxes
1997
Calix[4]arenes diametrically substituted at the upper rim with two melamine units spontaneously form well-defined box-like assemblies in the presence of two equivalents of 5,5-diethylbarbituric acid. These assemblies, consisting of nine different components, are held together by 36 hydrogen bonds and are stable in apolar solvents at concentrations of up to 10-4M. This paper reports the first X-ray crystal structure, and the MALDI TOF mass spectra together with the complete 1H NMR spectroscopic characterization of these hydrogen-bonded assemblies. The crystal structure clearly shows that the assemblies are stereogenic, as a result of the antiparallel orientation of the two rosette motifs. Fu…
Modeling Supramolecular Polymerization: The Role of Steric Effects and Hydrophobic Interactions
2019
We present a combined experimental–simulation study of self-assembly into one-dimensional filaments. Experimentally, we study amphiphilic AuI-metallopeptides in neutral aqueous media. Our model foc...
A Self-Sorting Scheme Based on Tetra-Urea Calix[4]arenes
2009
Size and shape do matter: When dimerized in nonpolar solvents, an equimolar mixture of eleven tetra-urea calix[4]arenes with different wide-rim substituents self-sorts into only six out of 35 different homo- and heterodimers (see picture). Since the calixarene scaffold and the four urea units are the same in all cases, the self-sorting process is driven only by the cooperative action of steric requirements and stoichiometry.
Weak Intermolecular Anion–π Interactions in Pentafluorobenzyl-Substituted Ammonium Betaines
2012
A series of ammonium–carboxylate and ammonium–sulfonate betaines was synthesized and studied by single-crystal X-ray diffraction analysis to investigate the weak intermolecular interactions as well as the intramolecular interactions in the solid state. None of the expected intramolecular anion–π interactions could be observed, probably because of the steric demands and the reduced nucleophilicity of the anionic part of the betaines. Nevertheless, a weak intermolecular anion–π interaction between the anionic part of the betaine and the pentafluorophenyl unit is present in the structure of 5a.
Steric Constraints Induced Frustrated Growth of Supramolecular Nanorods in Water.
2015
A unique example of supramolecular polymerisation in water based on monomers with nanomolar affinities, which yield rod-like materials with extraordinarily high thermodynamic stability, yet of finite length, is reported. A small library of charge-neutral dendritic peptide amphiphiles was prepared, with a branched nonaphenylalanine-based core that was conjugated to hydrophilic dendrons of variable steric demand. Below a critical size of the dendron, the monomers assemble into nanorod-like polymers, whereas for larger dendritic side chains frustrated growth into near isotropic particles is observed. The supramolecular morphologies observed by electron microscopy, X-ray scattering and diffusio…
Tetrameric and Dimeric [N∙∙∙I+∙∙∙N] Halogen-Bonded Supramolecular Cages
2017
Tripodal N-donor ligands are used to form halogen-bonded assemblies via structurally analogous Ag+-complexes. Selective formation of discrete tetrameric I6L4 and dimeric I3L2 halonium cages, wherein multiple [N∙∙∙I+∙∙∙N] halogen bonds are used in concert, can be achieved by using sterically rigidified cationic tris(1-methyl-1-azonia-4-azabicyclo[2.2.2]octane)-mesitylene ligand, L1(PF6)3, and flexible ligand 1,3,5-tris(imidazole-1-ylmethyl)-2,4,6-trimethylbenzene, L2, respectively. The iodonium cages, I6L14(PF6)18 and I3L22(PF6)3, were obtained through the [N∙∙∙Ag+∙∙∙N] → [N∙∙∙I+∙∙∙N] cation exchange reaction between the corresponding Ag6L14(PF6)18 and Ag3L22(PF6)3 coordination cages, prepar…
Functionalized lipid tubules as tools for helical crystallization of proteins
1997
The development of functional supramolecular devices built by self-assembly of elementary molecules and with bioactive properties arouses considerable interest in the field of nanotechnology and new materials. We report here the formation of a new class of lipid tubules exhibiting both properties of molecular recognition and crystal formation for the protein streptavidin. These lipid tubules, made of biotin-containing dioctadecylamine molecules, are straight hollow cylinders with a constant diameter of 27 nm and variable length up to several micrometers. They are unilamellar with an inner diameter of about 16 nm, as shown by cryoelectron microscopy. Streptavidin binds to the biotinylated tu…
Dual-Mode Chiral Self-Assembly of Cone-Shaped Subphthalocyanine Aromatics
2020
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.0c07291
Synthesis and Topological Determination of Hexakis-Substituted 1,4-Ditritylbenzene and Nonakis-Substituted 1,3,5-Tritritylbenzene Derivatives: Buildi…
2012
Based on trityl moieties, novel organic building blocks have been prepared and structurally investigated. Substituted hexaphenyl-p-xylene (1,4-ditritylbenzene) as well as extended analogues thereof were prepared. Furthermore, a new family based on a 1,3,5-tritritylbenzene motif, connecting three trityl groups through a formal mesitylene unit, was developed. Both families were further converted through six- and nine-fold substitution reactions, respectively, to yield potent molecular building blocks for supramolecular assemblies.
Solvent-free ball-milling subcomponent synthesis of metallosupramolecular complexes.
2015
Subcomponent self-assembly from components A, B, C, D, and Fe(2+) under solvent-free conditions by self-sorting leads to the construction of three structurally different metallosupramolecular iron(II) complexes. Under carefully selected ball-milling conditions, tetranuclear [Fe4 (AD2 )6 ](4-) 22-component cage 1, dinuclear [Fe2 (BD2 )3 ](2-) 11-component helicate 2, and 5-component mononuclear [Fe(CD3 )](2+) complex 3 were prepared simultaneously in a one-pot reaction from 38 components. Through subcomponent substitution reaction by adding subcomponent B, the [Fe4 (AD2 )6 ](4-) cage converts quantitatively to the [Fe2 (BD2 )3 ](2-) helicate, which, in turn, upon addition of subcomponent C, …