Browse
Submit Data
Databases
API
Help

Dataset Information

24 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

A chiral self-sorting photoresponsive coordination cage based on overcrowded alkenes.

ABSTRACT: In recent years, increasing efforts have been devoted to designing new functional stimuli-responsive supramolecular assemblies. Here, we present three isomeric supramolecular coordination complexes consisting of a Pd2L4 stoichiometry. As shown by NMR, CD and X-ray studies, as well as DFT calculations, these complexes form cage-like structures by chiral self-sorting. Photochromic ligands derived from first generation molecular motors enable light-driven interconversion between the three isomers. Two of the isomers were able to form host-guest complexes opening up new prospects toward stimuli-controlled substrate binding and release.

SUBMITTER: Stuckhardt C

PROVIDER: S-EPMC6880828 | biostudies-literature | 2019

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

A chiral self-sorting photoresponsive coordination cage based on overcrowded alkenes.

Stuckhardt Constantin C Roke Diederik D Danowski Wojciech W Otten Edwin E Wezenberg Sander J SJ Feringa Ben L BL

Beilstein journal of organic chemistry 20191115

In recent years, increasing efforts have been devoted to designing new functional stimuli-responsive supramolecular assemblies. Here, we present three isomeric supramolecular coordination complexes consisting of a Pd2L4 stoichiometry. As shown by NMR, CD and X-ray studies, as well as DFT calculations, these complexes form cage-like structures by chiral self-sorting. Photochromic ligands derived from first generation molecular motors enable light-driven interconversion betwe ...[more]

PMID: 31807210

Similar Datasets

Chiral Self-sorting of Giant Cubic [8+12] Salicylimine Cage Compounds.

Project description:Chiral self-sorting is intricately connected to the complicated chiral processes observed in nature and no artificial systems of comparably complexity have been generated by chemists. However, only a few examples of purely organic molecules have been reported so far, where the self-sorting process could be controlled. Herein, we describe the chiral self-sorting of large cubic [8+12] salicylimine cage compounds based on a chiral TBTQ precursor. Out of 23 possible cage isomers only the enantiopure and a meso cage were observed to be formed, which have been unambiguously characterized by single crystal X-ray diffraction. Furthermore, by careful choice of solvent the formation of meso cage could be controlled. With internal diameters of din =3.3-3.5 nm these cages are among the largest organic cage compounds characterized and show very high specific surface areas up to approx. 1500 m2 g-1 after desolvation.

| S-EPMC8048989 | biostudies-literature

A self-assembled photoresponsive gel consisting of chiral nanofibers.

Project description:A novel compound based on a glutamic acid skeleton, containing azobenzene as a photoresponsive group and ureidopyrimidinone (UPy) as a connection site, was designed and synthesized. The monomer is capable of forming an organogel in nonpolar organic solvents and different types of nanostructures in other solvents. The state of the gel and the chirality of the nanostructures could both be adjusted by subsequent light irradiation at different wavelengths. The helical nanofiber-like morphology was verified in the internal structure of the gel. The performance of this gel was investigated by a series of methods, such as UV-vis absorption spectroscopy, circular dichroism, scanning electron microscopy and rheological techniques. This work provides a new method for facile synthesis of chiro-optical gels.

| S-EPMC6122117 | biostudies-literature

Chiral Self-Discrimination and Guest Recognition in Helicene-Based Coordination Cages.

Project description:Chiral nanosized confinements play a major role for enantioselective recognition and reaction control in biological systems. Supramolecular self-assembly gives access to artificial mimics with tunable sizes and properties. Herein, a new family of [Pd2 L4 ] coordination cages based on a chiral [6]helicene backbone is introduced. A racemic mixture of the bis-monodentate pyridyl ligand L1 selectively assembles with PdII cations under chiral self-discrimination to an achiral meso cage, cis-[Pd2 L1P 2 L1M 2 ]. Enantiopure L1 forms homochiral cages [Pd2 L1P/M 4 ]. A longer derivative L2 forms chiral cages [Pd2 L2P/M 4 ] with larger cavities, which bind optical isomers of chiral guests with different affinities. Owing to its distinct chiroptical properties, this cage can distinguish non-chiral guests of different lengths, as they were found to squeeze or elongate the cavity under modulation of the helical pitch of the helicenes. The CD spectroscopic results were supported by ion mobility mass spectrometry.

| S-EPMC6563462 | biostudies-literature

Chiral self-sorting and guest recognition of porous aromatic cages.

Project description:The synthesis of ultra-stable chiral porous organic cages (POCs) and their controllable chiral self-sorting at the molecular and supramolecular level remains challening. Herein, we report the design and synthesis of a serial of axially chiral porous aromatic cages (PAC 1-S and 1-R) with high chemical stability. The theoretical and experimental studies on the chiral self-sorting reveal that the exclusive self-recognition on cage formation is an enthalpy-driven process while the chiral narcissistic and self-sorting on supramolecular assembly of racemic cages can be precisely regulated by π-π and C-H…π interactions from different solvents. Regarding the chemical stability, the crystallinity of PAC 1 is maintained in aqueous solvents, such as boiling water, high-concentrated acid and alkali; mixtures of solvents, such as 1 M H2SO4/MeOH/H2O solution, are also tolerated. Investigations on the chiral sensing performance show that PAC 1 enables enantioselective recognition of axially chiral biaryl molecules.

| S-EPMC9273608 | biostudies-literature

Fast synthesis and redox switching of di- and tetra-substituted bisthioxanthylidene overcrowded alkenes.

Project description:A rapid and efficient method for the synthesis of overcrowded alkenes using (trimethylsilyl)diazomethane provides a range of substituted bisthioxanthylidenes. We show large conformational redox switching from folded to orthogonal states, which tolerates many substitution patterns. The facile access to bisthioxanthylidene switches with the potential for further functionalization, in combination with the reliable redox chemistry, provides major opportunities for the design of electrochemically responsive systems.

| S-EPMC8330637 | biostudies-literature

Coordination-Cage-Catalysed Hydrolysis of Organophosphates: Cavity- or Surface-Based?

Project description:The hydrophobic central cavity of a water-soluble M8 L12 cubic coordination cage can accommodate a range of phospho-diester and phospho-triester guests such as the insecticide "dichlorvos" (2,2-dichlorovinyl dimethyl phosphate) and the chemical warfare agent analogue di(isopropyl) chlorophosphate. The accumulation of hydroxide ions around the cationic cage surface due to ion-pairing in solution generates a high local pH around the cage, resulting in catalysed hydrolysis of the phospho-triester guests. A series of control experiments unexpectedly demonstrates that-in marked contrast to previous cases-it is not necessary for the phospho-triester substrates to be bound inside the cavity for catalysed hydrolysis to occur. This suggests that catalysis can occur on the exterior surface of the cage as well as the interior surface, with the exterior-binding catalysis pathway dominating here because of the small binding constants for these phospho-triester substrates in the cage cavity. These observations suggest that cationic but hydrophobic surfaces could act as quite general catalysts in water by bringing substrates into contact with the surface (via the hydrophobic effect) where there is also a high local concentration of anions (due to ion pairing/electrostatic effects).

| S-EPMC7079011 | biostudies-literature

Self-assembly of a water-soluble endohedrally functionalized coordination cage including polar guests.

Project description:Coordination cages containing endohedrally functionalized aromatic cavities are scarce in the literature. Herein, we report the self-assembly of a tetra-cationic super aryl-extended calix[4]pyrrole tetra-pyridyl ligand into a water-soluble Pd(ii)-cage featuring two endohedral polar binding sites. They are defined by the four pyrrole NHs of the calix[4]pyrrole unit and the four inwardly directed α-protons of the coordinated pyridyl groups. The efficient assembly of the Pd(ii)-cage requires the inclusion of mono- and ditopic pyridyl N-oxide and aliphatic formamide guests. The monotopic guests only partially fill the cage's cavity and require the co-inclusion of a water molecule that is likely hydrogen-bonded to the endohedral α-pyridyl protons. The ditopic guests are able to completely fill the cage's cavity and complement both binding sites. We observed high conformational selectivity in the inclusion of the isomers of α,ω-bis-formamides. We briefly investigate the uptake and release mechanism/kinetics of selected polar guests by the Pd(ii)-cage using pair-wise competition experiments.

| S-EPMC8528040 | biostudies-literature

Photoresponsive supramolecular coordination polyelectrolyte as smart anticounterfeiting inks.

Project description:While photoluminescence printing is a widely applied anticounterfeiting technique, there are still challenges in developing new generation anticounterfeiting materials with high security. Here we report the construction of a photoresponsive supramolecular coordination polyelectrolyte (SCP) through hierarchical self-assembly of lanthanide ion, bis-ligand and diarylethene unit, driven by metal-ligand coordination and ionic interaction. Owing to the conformation-dependent photochromic fluorescence resonance energy transfer between the lanthanide donor and diarylethene acceptor, the ring-closure/ring-opening isomerization of the diarylethene unit leads to a photoreversible luminescence on/off switch in the SCP. The SCP is then utilized as security ink to print various patterns, through which photoreversible multiple information patterns with visible/invisible transformations are realized by simply alternating the irradiation with UV and visible light. This work demonstrates the possibility of developing a new class of smart anticounterfeiting materials, which could be operated in a noninvasive manner with a higher level of security.

| S-EPMC7921134 | biostudies-literature

Narcissistic, Integrative, and Kinetic Self-Sorting within a System of Coordination Cages.

Project description:Many useful principles of self-assembly have been elucidated through studies of systems where multiple components combine to create a single structure. More complex systems, where multiple product structures self-assemble in parallel from a shared set of precursors, are also of great interest, as biological systems exhibit this behavior. The greater complexity of such systems leads to an increased likelihood that discrete species will not be formed, however. Here we show how the kinetics of self-assembly govern the formation of multiple metal-organic architectures from a mixture of five building blocks, preventing the formation of a discrete structure of intermediate size. By varying ligand symmetry, denticity, and orientation, we explore how five distinct polyhedra-a tetrahedron, an octahedron, a cube, a cuboctahedron, and a triangular prism-assemble in concert around CoII template ions. The underlying rules dictating the organization of assemblies into specific shapes are deciphered, explaining the formation of only three discrete entities when five could form in principle.

| S-EPMC7304868 | biostudies-literature

N-Centered Chiral Self-Sorting and Supramolecular Helix of Troger's Base-Based Dimeric Macrocycles in Crystalline State.

Project description:Three stereoisomers of Tröger's Base-based dimeric macrocycles Trögerophane 1 (T1) including one pair of enantiomers ( rac-T1) and one meso isomer ( R 2N S 2N -T1) were obtained and fully characterized by X-ray analysis. In the crystalline stacking state R 2N S 2N -T1 showed heterochiral self-sorting behavior along a axis with cofacial π-π stacking interactions, while rac-T1 showed heterochiral self-sorting behavior along c axis with slipped π-π stacking interactions, respectively. Meanwhile both of them showed homochiral self-sorting behavior along b axis as well as one pair of supramolecular helixes were formed in both cases. All the self-sorting behaviors are controlled by two chiral Tröger's Base units from neighboring molecules. To the best of our knowledge, such chiral self-sorting and supramolecular helixes of N-centered chiral superstructures is a rare example. In addition, R 2N S 2N -T1 and rac-T1 demonstrated different adsorption capacities toward the vapor of dichloromethane and acetone, respectively.

| S-EPMC6555195 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data