Search results for "Supramolecular"
showing 10 items of 830 documents
Coordination Geometry Preference Regulates the Structure and Dynamics of Metallo-Supramolecular Polymer Networks
2021
Metal–ligand interactions are extensively used for the development of biomimetic polymers. Macroscopic properties of such systems are closely tied to the microscopic structure and dynamics of not o...
Structure of Polymers
2014
The structure and thermodynamics of polymers are discussed both with an adapted version of Flory’s regular solution theory and the concept of scaling and random walks. The salient properties of polymers like segregation and elasticity are discussed in terms of these concept. The Flory-Stockmayer theory of gelation is introduced and related to the percolation concept.
A Comparison of Shuttling Mechanisms in Two Constitutionally Isomeric Bistable Rotaxane-Based Sunlight-Powered Nanomotors
2006
To find out how best to optimize shuttling of the macrocycle in a particular class of photochemically driven molecular abacus, which has the molecular structure of BR-I6+ in its Mark I prototype (Ashton et al., Chem. Eur. J. 2000, 6, 3558), we have synthesized and characterized a Mark II version of this kind of two-station rotaxane comprised of six molecular modules, namely (a) a bisparaphenylene[34]crown-10 electron donor macrocycle M and its dumbbell-shaped component which contains (b) a Ru(ii)-polypyridine photoactive unit P2+ as one of its stoppers, (c) a p-terphenyl-type ring system as a rigid spacer S, (d) 4,4′-bipyridinium (A12+) and (e) 3,3′-dimethyl-4,4′-bipyridinium (A22+) electr…
Multiple interactions between molecular and supramolecular ordering
1999
We report studies of the interplay among processes of molecular conformational changes, spinodal demixing of the solution, and molecular crosslinking involved in the physical gelation of a biopolysaccharide-water system. Multiple interactions and kinetic competition among these processes were studied under largely different absolute and relative values of their individual rates by appropriate choices of the quenching temperature at constant polymer concentration. Quenching temperature strongly affects the rate of growth but not the final value of the fractal dimension of the gel. Kinetic competition plays a central role in determining the final conformation of individual molecules and the s…
Receptors for Nucleotides
2012
Recognition and activation of nucleotides by polyammonium receptors constitute an important target in supramolecular chemistry since the very beginning of this field. Nucleotides have three components: (i) the polyphosphate chain, (ii) the sugar moiety, and (iii) the nucleobase, which permit their multipoint binding through attractions between opposite charges, hydrogen bonding, π-stacking, CH–π interactions, and so on. In this chapter, different receptors for nucleotides, most but not all of them consisting polyamines, are examined, focusing on their molecular structure that enables different binding modes to be operated. Also, a number of examples of nucleotide binding through metal compl…
Binding motif of ebselen in solution: Chalcogen and hydrogen bonds team up
2020
Ebselen (2-phenyl-1,2-benzoselenazol-3(2H)one), a glutathione peroxidase mimic, is active against several RNA viruses, among others the retrovirus responsible for the COVID-19 pandemic. In this paper 77Se and 1H NMR studies of ebselen are reported and they identify the chalcogen bond (ChB) and hydrogen bond (HB) that are central in the landscape of interactions formed by the compound in solution. The selenium atom and the hydrogen atom at the C7 carbon act as ChB and HB donors and the O and N atoms of neutral molecules function as acceptors. The ChB and HB give rise to a bifurcated supramolecular synthon, which fastens the interaction acceptor opposite to the N–Se covalent bond of the selen…
Tri- and tetraurea piperazine cyclophanes: synthesis and complexation studies of preorganized and folded receptor molecules.
2010
A series of symmetrical tri- and tetrameric N-ethyl- and N-phenylurea-functionalized cyclophanes have been prepared in nearly quantitative yields (86-99 %) from the corresponding tri- and tetraamino-functionalized piperazine cyclophanes and ethyl or phenyl isocyanates. Their conformational and complexation properties have been studied by single-crystal X-ray diffraction, variable-temperature NMR spectroscopy, and ESI-MS analysis. The rigid 27-membered trimeric cyclophane skeleton assisted by a seam of intramolecular hydrogen bonds results in a preorganized ditopic recognition site with an all-syn conformation of the urea moieties that, complemented by a lipophilic cavity of the cyclophane, …
Controlling Multivalent Interactions in Triply-Threaded Two-Component Superbundles
2003
We have investigated the (1)H NMR spectra, the absorption spectra, the fluorescence spectra and decays, and the electrochemical properties of i). a tritopic receptor in which three benzo[24]crown-8 macrorings are fused onto a triphenylene core, ii). a trifurcated trication wherein three dibenzylammonium ions are linked 1,3,5 to a central benzenoid core, and iii). their 1:1 adduct which constitutes a triply-threaded, two-component supramolecular bundle. X-Ray crystallography has established the precise geometry of this paucivalent recognition motif in the solid state. In addition to [N(+)-H...O] hydrogen bonding and [C-H...O] interactions between the NH(2) (+) centers on the three dibenzylam…
Recognition-Directed Supramolecular Assemblies of Metal Complexes of Terpyridine Derived Ligands with Self-Complementary Hydrogen Bonding Sites
2000
The synthesis and X-ray structures of three metal complexes with terpyridine-derived ligands that contain amino-pyrimidine and amino-pyrazine moieties are presented. They have been designed in view of directing their self-assembly into specific supramolecular arrays through molecular recognition interactions. The solid-state structures indeed reveal extensive hydrogen-bonded networks. The Co complex 4a with PF6- counterions builds a two-dimensional infinite interwoven grid through strong double hydrogen bonds (d(N-H-N) =2.918-3.018 A) between the amino groups and the N atoms of the rings, with all H-bonding sites saturated. Changing the anions to BF4- in 4b leads to a similar infinite but p…
Generation of [2×2] Grid Metallosupramolecular Architectures from Preformed Ditopic Bis(acylhydrazone) Ligands and through Component Self‐Assembly
2007
Ditopic bis(acylhydrazone) ligands, derived from the reactions of carbohydrazides with 2-phenylpyrimidine-4,6-dicarbaldehyde and designed for grid formation with octahedrally coordinating transition-metal ions, exhibit a varied coordination chemistry depending upon the degree of their deprotonation. The neutral acylhydrazones are relatively poor ligands and are seemingly involved in multiple, labile complexation equilibria varying with the solvent and the particular metal salt in solution; nevertheless, grid complexes of different forms can be isolated in the solid state. Although only limited study has been made of the singly deprotonated ligands, grid species appear to be much more readil…