Browse
Submit Data
Databases
API
Help

Dataset Information

27 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Porous shape-persistent rylene imine cages with tunable optoelectronic properties and delayed fluorescence.

ABSTRACT: A simultaneous combination of porosity and tunable optoelectronic properties, common in covalent organic frameworks, is rare in shape-persistent organic cages. Yet, organic cages offer important molecular advantages such as solubility and modularity. Herein, we report the synthesis of a series of chiral imine organic cages with three built-in rylene units by means of dynamic imine chemistry and we investigate their textural and optoelectronic properties. Thereby we demonstrate that the synthesized rylene cages can be reversibly reduced at accessible potentials, absorb from UV up to green light, are porous, and preferentially adsorb CO₂ over N₂ and CH₄ with a good selectivity. In addition, we discovered that the cage incorporating three perylene-3,4:9,10-bis(dicarboximide) units displays an efficient delayed fluorescence. Time-correlated single photon counting and transient absorption spectroscopy measurements suggest that the delayed fluorescence is likely a consequence of a reversible intracage charge-separation event. Rylene cages thus offer a promising platform that allows combining the porosity of processable materials and photochemical phenomena useful in diverse applications such as photocatalysis or energy storage.

SUBMITTER: Huang HH

PROVIDER: S-EPMC8179562 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Soluble Congeners of Prior Insoluble Shape-Persistent Imine Cages.

Project description:One of the most applied reaction types to synthesize shape-persistent organic cage compounds is the imine condensation reaction and it is assumed that the formed cages are thermodynamically controlled products due to the reversibility of the imine condensation. However, most of the synthesized imine cages reported are formed as precipitate from the reaction mixture and therefore rather may be kinetically controlled products. There are even examples in literature, where resulting cages are not soluble at all in common organic solvents to characterize or study their formation by NMR spectroscopy in solution. Here, a triptycene triamine containing three solubilizing n-hexyloxy chains has been used to synthesize soluble congeners of prior insoluble cages. This allowed us to study the formation as well as the reversibility of cage formation in solution by investigating exchange of building blocks between the cages and deuterated derivatives thereof.

| S-EPMC8362185 | biostudies-literature

Shape-Persistent [4+4] Imine Cages with a Truncated Tetrahedral Geometry.

Project description:The synthesis of shape-persistent organic cage compounds is often based on the usage of multiple dynamic covalent bond formation (such as imines) of readily available precursors. By careful choice of the precursors geometry, the geometry and size of the resulting cage can be accurately designed and indeed a number of different geometries and sizes have been realized to date. Despite of this fact, little is known about the precursors conformational rigidity and steric preorganization of reacting functional groups on the outcome of the reaction. Herein, the influence of conformational rigidity in the precursors on the formation of a [4+4] imine cage with truncated tetrahedral geometry is discussed.

| S-EPMC5838406 | biostudies-literature

Transformation of Imine Cages into Hydrocarbon Cages.

Project description:In contrast to organic cages which are formed by exploiting dynamic covalent chemistry, such as boronic ester cages, imine cages, or disulfide cages, those with a fully carbonaceous backbone are rarer. With the exception of alkyne metathesis based approaches, the vast majority of hydrocarbon cages need to be synthesized by kinetically controlled bond formation. This strategy implies a multiple step synthesis and no correction mechanism in the final macrocyclization step, both of which are responsible for low overall yields. Whereas for smaller cages the intrinsic drawbacks are not always obvious, larger cages are seldom synthesized in yields beyond a few tenths of a percent. Presented herein is a three-step method to convert imine cages into hydrocarbon cages. The method has been successfully applied to even larger structures such as derivatives of C72 H72 , an unknown cage suggested by Fritz Vögtle more than 20 years ago.

| S-EPMC6470955 | biostudies-literature

Cucurbitimines - imine cages with concave walls.

Project description:The variety of shape-persistent organic cages by imine bond formation has tremendously enlarged in recent years by using different building blocks (aldehydes and amines) in the condensation reactions. Here, we describe the use of a kinked tetraldehyde to generate pumpkin-shaped cages with concave walls, similar to cucurbiturils.

| S-EPMC8276630 | biostudies-literature

Persistent Dimer Emission in Thermally Activated Delayed Fluorescence Materials.

Project description:We expose significant changes in the emission color of carbazole-based thermally activated delayed fluorescence (TADF) emitters that arise from the presence of persistent dimer states in thin films and organic light-emitting diodes (OLEDs). Direct photoexcitation of this dimer state in 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) reveals the significant influence of dimer species on the color purity of its photoluminescence and electroluminescence. The dimer species is sensitive to the sample preparation method, and its enduring presence contributes to the widely reported concentration-mediated red shift in the photoluminescence and electroluminescence of evaporated thin films. This discovery has implications on the usability of these, and similar, molecules for OLEDs and explains disparate electroluminescence spectra presented in the literature for these compounds. The dimerization-controlled changes observed in the TADF process and photoluminescence efficiency mean that careful consideration of dimer states is imperative in the design of future TADF emitters and the interpretation of previously reported studies of carbazole-based TADF materials.

| S-EPMC6501699 | biostudies-literature

A general supramolecular strategy for fabricating full-color-tunable thermally activated delayed fluorescence materials

Project description: Not available

| S-EPMC10873404 | biostudies-literature

Core-Shell Crystals of Porous Organic Cages.

Project description:The first examples of core-shell porous molecular crystals are described. The physical properties of the core-shell crystals, such as surface hydrophobicity, CO2 ?/CH4 selectivity, are controlled by the chemical composition of the shell. This shows that porous core-shell molecular crystals can exhibit synergistic properties that out-perform materials built from the individual, constituent molecules.

| S-EPMC6120484 | biostudies-literature

Water-stable hydrazone-linked porous organic cages.

Project description:Although porous organic cages (POCs), particularly imine-linked (C[double bond, length as m-dash]N) ones, have advanced significantly over the last few decades, the reversible nature of imine linkages makes them prone to hydrolysis and structural collapse, severely limiting their applications under moist or water conditions. Herein, seven water-stable hydrazone-linked (C[double bond, length as m-dash]N-N) POCs are prepared through a simple coupling of the same supramolecular tetraformylresorcin[4]arene cavitand with different dihydrazide linkers. Their structures are all determined by single-crystal X-ray crystallography, demonstrating rich structural diversity from the [2 + 4] lantern, [3 + 6] triangular prism, and unprecedented [4 + 8] square prism to the extra-large [6 + 12] octahedron. In addition, they respectively exhibit tunable window diameters and cavity volumes ranging from about 5.4 to 11.1 nm and 580 to 6800 Å3. Moreover, their application in the water environment for pollutant removal was explored, indicating that they can effectively eliminate various types of contaminants from water, including radionuclide waste, toxic heavy metal ions, and organic micropollutants. This work demonstrates a convenient method for rationally constructing versatile robust POCs and presents their great application potentialities in water medium.

| S-EPMC8528071 | biostudies-literature

Porous organic cages as synthetic water channels.

Project description:Nature has protein channels (e.g., aquaporins) that preferentially transport water molecules while rejecting even the smallest hydrated ions. Aspirations to create robust synthetic counterparts have led to the development of a few one-dimensional channels. However, replicating the performance of the protein channels in these synthetic water channels remains a challenge. In addition, the dimensionality of the synthetic water channels also imposes engineering difficulties to align them in membranes. Here we show that zero-dimensional porous organic cages (POCs) with nanoscale pores can effectively reject small cations and anions while allowing fast water permeation (ca. 109 water molecules per second) on the same magnitude as that of aquaporins. Water molecules are found to preferentially flow in single-file, branched chains within the POCs. This work widens the choice of water channel morphologies for water desalination applications.

| S-EPMC7530991 | biostudies-literature

Porous Organic Cages for Sulfur Hexafluoride Separation.

Project description:A series of porous organic cages is examined for the selective adsorption of sulfur hexafluoride (SF6) over nitrogen. Despite lacking any metal sites, a porous cage, CC3, shows the highest SF6/N2 selectivity reported for any material at ambient temperature and pressure, which translates to real separations in a gas breakthrough column. The SF6 uptake of these materials is considerably higher than would be expected from the static pore structures. The location of SF6 within these materials is elucidated by X-ray crystallography, and it is shown that cooperative diffusion and structural rearrangements in these molecular crystals can rationalize their superior SF6/N2 selectivity.

| S-EPMC5101576 | 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