Browse
Submit Data
Databases
API
Help

Dataset Information

28 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Tiara[5]arenes: Synthesis, Solid-State Conformational Studies, Host-Guest Properties, and Application as Nonporous Adaptive Crystals.

ABSTRACT: Tiara[5]arenes (T[5]s), a new class of five-fold symmetric oligophenolic macrocycles that are not accessible from the addition of formaldehyde to phenol, were synthesized for the first time. These pillar[5]arene-derived structures display both unique conformational freedom, differing from that of pillararenes, with a rich blend of solid-state conformations and excellent host-guest interactions in solution. Finally we show how this novel macrocyclic scaffold can be functionalized in a variety of ways and used as functional crystalline materials to distinguish uniquely between benzene and cyclohexane.

SUBMITTER: Yang W

PROVIDER: S-EPMC7187373 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Tiara[5]arenes: Synthesis, Solid-State Conformational Studies, Host-Guest Properties, and Application as Nonporous Adaptive Crystals.

Yang Weiwei W Samanta Kushal K Wan Xintong X Thikekar Tushar Ulhas TU Chao Yang Y Li Shunshun S Du Ke K Xu Jun J Gao Yan Y Zuilhof Han H Sue Andrew C-H AC

Angewandte Chemie (International ed. in English) 20200121 10

Tiara[5]arenes (T[5]s), a new class of five-fold symmetric oligophenolic macrocycles that are not accessible from the addition of formaldehyde to phenol, were synthesized for the first time. These pillar[5]arene-derived structures display both unique conformational freedom, differing from that of pillararenes, with a rich blend of solid-state conformations and excellent host-guest interactions in solution. Finally we show how this novel macrocyclic scaffold can be functionalized in a variety of ...[more]

PMID: 31763754

Similar Datasets

Cyclic Ether Contaminant Removal from Water Using Nonporous Adaptive Pillararene Crystals via Host-Guest Complexation at the Solid-Solution Interface.

Project description:The removal of soluble cyclic ether contaminants, such as dioxane and THF, produced in industrial chemical processes from water is of great importance for environmental protection and human health. Here we report that nonporous adaptive crystals of perethylated pillar[5]arene (EtP5) and pillar[6]arene (EtP6) work as adsorbents for cyclic ether contaminant removal via host-guest complexation at the solid-solution interface. Nonporous EtP6 crystals have the ability to adsorb dioxane from water with the formation of 1:2 host-guest complex crystals, while EtP5 crystals cannot. However, both guest-free EtP5 and EtP6 crystals remove THF from water with EtP5 having a better capacity. This is because EtP5 forms a 1:2 host-guest complex with THF via host-guest complexation at the solid-solution interface while EtP6 forms a 1:1 host-guest complex with THF. EtP6 also shows the ability to selectively remove dioxane from water even in the presence of THF. Moreover, the reversible transitions between nonporous guest-free EtP5 and EtP6 structures and guest-loaded structures make them highly recyclable.

| S-EPMC6750096 | biostudies-literature

Capture of Sulfur Mustard by Pillar[5]arene: From Host-Guest Complexation to Efficient Adsorption Using Nonporous Adaptive Crystals.

Project description:Sulfur mustard (SM) has been the most frequently used chemical warfare agent. Here, we present the efficient containment of SM and its simulants by per-ethylated pillar[5]arene (EtP5). EtP5 exhibited strong binding abilities toward SM and its simulants not only in solution but also in the solid state. The association constant (Ka) between SM and EtP5 was determined as (6.2 ± 0.6) × 103 M-1 in o-xylene-d10. Single crystal structure of SM@EtP5 showed that a 1:1 inclusion complex was formed, which was driven by multiple C-H···π/Cl/S and S···π interactions. In addition, activated crystal materials of EtP5 (EtP5α) could effectively adsorb SM simulants at solid-vapor phase; powder X-ray diffraction patterns and host-guest crystal structures indicated that the uptake process triggered a solid-state structural transformation. More interestingly, the captured guest molecules could be stably contained in EtP5α for at least 6 months in air at room temperature.

| S-EPMC7452326 | biostudies-literature

Adsorptive separation of cyclohexanol and cyclohexanone by nonporous adaptive crystals of RhombicArene.

Project description:As feedstock chemicals with similar boiling points, cyclohexanol (CHOL) and cyclohexanone (CHON) are often obtained as mixtures during production processes. Separation of mixed CHOL and CHON is important but energy-consuming by distillation. Here we report the development of a new macrocycle RhombicArene, which forms a host-guest complex with CHON through C-H⋯π interactions and hydrogen bonds. The nonporous adaptive crystals of RhombicArene exhibit excellent capability for rapid (30 minutes), exclusive (>99.9%), and recyclable vapor adsorption of CHON in the presence of CHOL under mild and user-friendly conditions.

| S-EPMC8654018 | biostudies-literature

Rim-Differentiated C<sub>5</sub>-Symmetric Tiara-Pillar[5]arenes.

Project description:The synthesis of "rim-differentiated" C5-symmetric pillar[5]arenes, whose two rims are decorated with different chemical functionalities, has remained a challenging task. This is due to the inherent statistical nature of the cyclization of 1,4-disubstituted alkoxybenzenes with different substituents, which leads to four constitutional isomers with only 1/16th being rim-differentiated. Herein, we report a "preoriented" synthetic protocol based on FeCl3-catalyzed cyclization of asymmetrically substituted 2,5-dialkoxybenzyl alcohols. This yields an unprecedented 55% selectivity of the C5-symmetric tiara-like pillar[5]arene isomer among four constitutional isomers. Based on this new method, a series of functionalizable tiara-pillar[5]arene derivatives with C5-symmetry was successfully synthesized, isolated, and fully characterized in the solid state.

| S-EPMC5765533 | biostudies-literature

A Luminescent Guest@MOF Nanoconfined Composite System for Solid-State Lighting.

Project description:A series of rhodamine B (RhB) encapsulated zeolitic imidazolate framework-8 (RhB@ZIF-8) composite nanomaterials with different concentrations of guest loadings have been synthesized and characterized in order to investigate their applicability to solid-state white-light-emitting diodes (WLEDs). The nanoconfinement of the rhodamine B dye (guest) in the sodalite cages of ZIF-8 (host) is supported by fluorescence spectroscopic and photodynamic lifetime data. The quantum yield (QY) of the luminescent RhB@ZIF-8 material approaches unity when the guest loading is controlled at a low level: 1 RhB guest per ~7250 cages. We show that the hybrid (luminescent guest) LG@MOF material, obtained by mechanically mixing a suitably high-QY RhB@ZIF-8 red emitter with a green-emitting fluorescein@ZIF-8 "phosphor" with a comparably high QY, could yield a stable, intensity tunable, near-white light emission under specific test conditions described. Our results demonstrate a novel LG@MOF composite system exhibiting a good combination of photophysical properties and photostability, for potential applications in WLEDs, photoswitches, bioimaging and fluorescent sensors.

| S-EPMC8706567 | biostudies-literature

State- and water repellency-controllable molecular glass of pillar[5]arenes with fluoroalkyl groups by guest vapors.

Project description:Molecular glasses are low-molecular-weight organic compounds that are stable in the amorphous state at room temperature. Herein, we report a state- and water repellency-controllable molecular glass by n-alkane guest vapors. We observed that a macrocyclic host compound pillar[5]arene with the C2F5 fluoroalkyl groups changes from the crystalline to the amorphous state (molecular glass) by heating above its melting point and then cooling to room temperature. The pillar[5]arene molecular glass shows reversible transitions between amorphous and crystalline states by uptake and release of the n-alkane guest vapors, respectively. Furthermore, the n-alkane guest vapor-induced reversible changes in the water contact angle were also observed: water contact angles increased and then reverted back to the original state by the uptake and release of the n-alkane guest vapors, respectively, along with the changes in the chemical structure and roughness on the surface of the molecular glass. The water repellency of the molecular glass could be controlled by tuning the uptake ratio of the n-alkane guest vapor.

| S-EPMC8985507 | biostudies-literature

A conformationally adaptive macrocycle: conformational complexity and host-guest chemistry of zorb[4]arene.

Project description:Large amplitude conformational change is one of the features of biomolecular recognition and is also the basis for allosteric effects and signal transduction in functional biological systems. However, synthetic receptors with controllable conformational changes are rare. In this article, we present a thorough study on the host-guest chemistry of a conformationally adaptive macrocycle, namely per-O-ethoxyzorb[4]arene (ZB4). Similar to per-O-ethoxyoxatub[4]arene, ZB4 is capable of accommodating a wide range of organic cations. However, ZB4 does not show large amplitude conformational responses to the electronic substituents on the guests. Instead of a linear free-energy relationship, ZB4 follows a parabolic free-energy relationship. This is explained by invoking the influence of secondary C-H···O hydrogen bonds on the primary cation···? interactions based on the information obtained from four representative crystal structures. In addition, heat capacity changes (?Cp) and enthalpy-entropy compensation phenomena both indicate that solvent reorganization is also involved during the binding. This research further deepens our understanding on the binding behavior of ZB4 and lays the basis for the construction of stimuli-responsive materials with ZB4 as a major component.

| S-EPMC6037019 | biostudies-other

Dynamics in Flexible Pillar[<i>n</i>]arenes Probed by Solid-State NMR.

Project description:Pillar[n]arenes are supramolecular assemblies that can perform a range of technologically important molecular separations which are enabled by their molecular flexibility. Here, we probe dynamical behavior by performing a range of variable-temperature solid-state NMR experiments on microcrystalline perethylated pillar[n]arene (n = 5, 6) and the corresponding three pillar[6]arene xylene adducts in the 100-350 K range. This was achieved either by measuring site-selective motional averaged 13C 1H heteronuclear dipolar couplings and subsequently accessing order parameters or by determining 1H and 13C spin-lattice relaxation times and extracting correlation times based on dipolar and/or chemical shift anisotropy relaxation mechanisms. We demonstrate fast motional regimes at room temperature and highlight a significant difference in dynamics between the core of the pillar[n]arenes, the protruding flexible ethoxy groups, and the adsorbed xylene guest. Additionally, unexpected and sizable 13C 1H heteronuclear dipolar couplings for a quaternary carbon were observed for p-xylene adsorbed in pillar[6]arene only, indicating a strong host-guest interaction and establishing the p-xylene location inside the host, confirming structural refinements.

| S-EPMC8237263 | biostudies-literature

Switching of the solid-state guest selectivity: solvent-dependent selective guest inclusion in a crystalline macrocyclic boronic ester.

Project description:Selective inclusion of each of bicyclic and tricyclic aromatic guest molecules was realized utilizing the self-assembly of a crystalline benzothiadiazole-type macrocyclic boronic ester. The complete switching of the guest selectivity was achieved simply by changing the cosolvent used in the formation of the crystalline host-guest complexes. Both the association free energy of host-guest complexes and the stability of packing structure were found to play important roles for the determination of the guest selectivity in this system, and the critical role of solvent molecules in the crystalline state for the switching phenomena was clarified.

| S-EPMC6054024 | biostudies-literature

Quantifying conformational dynamics using solid-state R₁ρ experiments.

Project description:We demonstrate the determination of quantitative rates of molecular reorientation in the solid state with rotating frame (R(1ρ)) relaxation measurements. Reorientation of the carbon chemical shift anisotropy (CSA) tensor was used to probe site-specific conformational exchange in a model system, d(6)-dimethyl sulfone (d(6)-DMS). The CSA as a probe of exchange has the advantage that it can still be utilized when there is no dipolar mechanism (i.e. no protons attached to the site of interest). Other works have presented R(1ρ) measurements as a general indicator of dynamics, but this study extracts quantitative rates of molecular reorientation from the R(1ρ) values. Some challenges of this technique include precise knowledge of sample temperature and determining the R(2)(0) contribution to the observed relaxation rate from interactions other than molecular reorientation, such as residual dipolar couplings or fast timescale dynamics; determination of this term is necessary in order to quantify the exchange rate due to covariance between the 2 terms. Low-temperature experiments measured an R(2)(0) value of 1.8±0.2s(-1) Allowing for an additional relaxation term (R(2)(0)), which was modeled as both temperature-dependent and temperature-independent, rates of molecular reorientation were extracted from field strength-dependent R(1ρ) measurements at four different temperatures and the activation energy was determined from these exchange rates. The activation energies determined were 74.7±4.3kJ/mol and 71.7±2.9kJ/mol for the temperature-independent and temperature-dependent R(2)(0) models respectively, in excellent agreement with literature values. The results of this study suggest important methodological considerations for the application of the method to more complicated systems such as proteins, such as the importance of deuterating samples and the need to make assumptions regarding the R(2)(0) contribution to relaxation.

| S-EPMC3572234 | 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