Browse
Submit Data
Databases
API
Help

Dataset Information

10 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Metal-organic tube or layered assembly: reversible sheet-to-tube transformation and adaptive recognition.

ABSTRACT: Rational preparation of an adaptive cavity-like enzyme is a great challenge for chemists. Herein, a new self-assembly strategy for the rational preparation of metal-organic tubes with nano-channels has been developed; both 1D metal-organic tube and corresponding 2D layered assemblies can be selectively synthesized driven by different templates; reversible sheet-to-tube transformation can be realized and the key intermediate has been identified. Furthermore, the newly formed nano-channel displays excellent polarity-selectivity for encapsulation of guest molecules, and can be further expanded or contracted through guest-driven adaptive deformation; even induced by very similar guest molecules, the adaptive deformations can also be obviously distinguished. Finally, the key chemicals benzene/hexane with a similar size can also be effectively separated by such nano-channels in the liquid phase. Our work not only provides a new synthetic strategy for the rational synthesis of metal-organic tubes with a reversible sheet-to-tube transformation character, but also gives a potential method for the construction of adaptive host-like enzymes and an in-depth understanding of the nature of adaptive host and guest molecules.

SUBMITTER: Tian J

PROVIDER: S-EPMC8162108 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Triggered reversible phase transformation between layered and spinel structure in manganese-based layered compounds.

Project description:Irreversible phase transformation of layered structure into spinel structure is considered detrimental for most of the layered structure cathode materials. Here we report that this presumably irreversible phase transformation can be rendered to be reversible in sodium birnessite (NaxMnO2·yH2O) as a basic structural unit. This layered structure contains crystal water, which facilitates the formation of a metastable spinel-like phase and the unusual reversal back to layered structure. The mechanism of this phase reversibility was elucidated by combined soft and hard X-ray absorption spectroscopy with X-ray diffraction, corroborated by first-principle calculations and kinetics investigation. These results show that the reversibility, modulated by the crystal water content between the layered and spinel-like phases during the electrochemical reaction, could activate new cation sites, enhance ion diffusion kinetics and improve its structural stability. This work thus provides in-depth insights into the intercalating materials capable of reversible framework changes, thereby setting the precedent for alternative approaches to the development of cathode materials for next-generation rechargeable batteries.

| S-EPMC6718664 | biostudies-literature

Reversible multicolor chromism in layered formamidinium metal halide perovskites.

Project description:Metal halide perovskites feature crystalline-like electronic band structures and liquid-like physical properties. The crystal-liquid duality enables optoelectronic devices with unprecedented performance and a unique opportunity to chemically manipulate the structure with low energy input. In this work, we leverage the low formation energy of metal halide perovskites to demonstrate multicolor reversible chromism. We synthesized layered Ruddlesden-Popper FAn+1PbnX3n+1 (FA = formamidinium, X = I, Br; n = number of layers = 1, 2, 3 … ∞) and reversibly tune the dimensionality (n) by modulating the strength and number of H-bonds in the system. H-bonding was controlled by exposure to solvent vapor (solvatochromism) or temperature change (thermochromism), which shuttles FAX salt pairs between the FAn+1PbnX3n+1 domains and adjacent FAX "reservoir" domains. Unlike traditional chromic materials that only offer a single-color transition, FAn+1PbnX3n+1 films reversibly switch between multiple colors including yellow, orange, red, brown, and white/colorless. Each colored phase exhibits distinct optoelectronic properties characteristic of 2D superlattice materials with tunable quantum well thickness.

| S-EPMC7568568 | biostudies-literature

A semiconducting layered metal-organic framework magnet.

Project description:The realization of ferromagnetism in semiconductors is an attractive avenue for the development of spintronic applications. Here, we report a semiconducting layered metal-organic framework (MOF), namely K3Fe2[(2,3,9,10,16,17,23,24-octahydroxy phthalocyaninato)Fe] (K3Fe2[PcFe-O8]) with spontaneous magnetization. This layered MOF features in-plane full ?-d conjugation and exhibits semiconducting behavior with a room temperature carrier mobility of 15?±?2?cm2?V-1?s-1 as determined by time-resolved Terahertz spectroscopy. Magnetization experiments and 57Fe Mössbauer spectroscopy demonstrate the presence of long-range magnetic correlations in K3Fe2[PcFe-O8] arising from the magnetic coupling between iron centers via delocalized ? electrons. The sample exhibits superparamagnetic features due to a distribution of crystal size and possesses magnetic hysteresis up to 350?K. Our work sets the stage for the development of spintronic materials exploiting magnetic MOF semiconductors.

| S-EPMC6646349 | biostudies-literature

Adaptive self-assembly and induced-fit transformations of anion-binding metal-organic macrocycles.

Project description:Container-molecules are attractive to chemists due to their unique structural characteristics comparable to enzymes and receptors in nature. We report here a family of artificial self-assembled macrocyclic containers that feature induced-fit transformations in response to different anionic guests. Five metal-organic macrocycles with empirical formula of MnL2n (M=Metal; L=Ligand; n=3, 4, 5, 6, 7) are selectively obtained starting from one simple benzimidazole-based ligand and square-planar palladium(II) ions, either by direct anion-adaptive self-assembly or induced-fit transformations. Hydrogen-bonding interactions between the inner surface of the macrocycles and the anionic guests dictate the shape and size of the product. A comprehensive induced-fit transformation map across all the MnL2n species is drawn, with a representative reconstitution process from Pd7L14 to Pd3L6 traced in detail, revealing a gradual ring-shrinking mechanism. We envisage that these macrocyclic molecules with adjustable well-defined hydrogen-bonding pockets will find wide applications in molecular sensing or catalysis.

| S-EPMC5481752 | biostudies-literature

Reversible Atmospheric Water Harvesting Using Metal-Organic Frameworks.

Project description:The passive capture of clean water from humid air without reliance on bulky equipment and high energy has been a substantial challenge and has attracted significant interest as a potential environmentally friendly alternative to traditional water harvesting methods. Metal-organic frameworks (MOFs) offer a high potential for this application due to their structural versatility which permits scalable, facile modulations of structural and functional elements. Although MOFs are promising materials for water harvesting, little research has been done to address the microstructure-adsorbing characteristics relationship with respect to the dynamic adsorption-desorption process. In this article, we present a parametric study of nine hydrolytically stable MOFs with diverse structures for unraveling fundamental material properties that govern the kinetics of water sequestration in this class of materials as well as investigating overall uptake capacity gravimetrically. The effects of temperature, relative humidity, and powder bed thickness on the adsorption-desorption process are explored for achieving optimal operational parameters. We found that Zr-MOF-808 can produce up to 8.66 LH2O kg-1MOF day-1, an extraordinary finding that outperforms any previously reported values for MOF-based systems. The presented findings help to deepen our understanding and guide the discovery of next-generation water harvesting materials.

| S-EPMC6992632 | biostudies-literature

Metal-Organic Nanosheets Formed via Defect-Mediated Transformation of a Hafnium Metal-Organic Framework.

Project description:We report a hafnium-containing MOF, hcp UiO-67(Hf), which is a ligand-deficient layered analogue of the face-centered cubic fcu UiO-67(Hf). hcp UiO-67 accommodates its lower ligand:metal ratio compared to fcu UiO-67 through a new structural mechanism: the formation of a condensed "double cluster" (Hf12O8(OH)14), analogous to the condensation of coordination polyhedra in oxide frameworks. In oxide frameworks, variable stoichiometry can lead to more complex defect structures, e.g., crystallographic shear planes or modules with differing compositions, which can be the source of further chemical reactivity; likewise, the layered hcp UiO-67 can react further to reversibly form a two-dimensional metal-organic framework, hxl UiO-67. Both three-dimensional hcp UiO-67 and two-dimensional hxl UiO-67 can be delaminated to form metal-organic nanosheets. Delamination of hcp UiO-67 occurs through the cleavage of strong hafnium-carboxylate bonds and is effected under mild conditions, suggesting that defect-ordered MOFs could be a productive route to porous two-dimensional materials.

| S-EPMC5469521 | biostudies-literature

Reversible Mechanochromic Delayed Fluorescence in 2D Metal-Organic Micro/Nanosheets: Switching Singlet-Triplet States through Transformation between Exciplex and Excimer.

Project description:Mechanochromic luminescent materials have attracted much attention and present a variety of applications in information security, data recording, and storage devices. However, most of these smart luminescent systems are based on typical fluorescence and/or phosphorescence mechanisms; the mechanochromic delayed fluorescence (MCDF) materials involving switching singlet and triplet states are rarely studied to date. Herein, new 2D layered metal-organic micro/nanosheets, [Cd(9-AC)2(BIM)2] (named as MCDF-1; 9-AC = anthracene-9-carboxylate and BIM = benzimidazole) and its solvate form containing interlayer CH3CN (named as MCDF-2), which exhibit reversible mechanochromic delayed fluorescence characteristics, are presented. With applying the mechanical force, the luminescent center of MCDF-1 can be converted from 9-AC/BIM exciplex to 9-AC/9-AC excimer, resulting in alternations of delayed fluorescence. Such luminescent change can be further recovered by CH3CN fumigation, accompanied by the structural transformation from MCDF-1 to MCDF-2. Furthermore, the force-responsive process also refers to the energy redistribution between singlet and triplet states as inferred by both temperature-dependent photophysics and theoretical calculations. Therefore, this work not only develops new 2D micro/nanosheets as MCDF materials, but also supplies a singlet-triplet energy switching mechanism on their reversible mechanochromic process.

| S-EPMC6247076 | biostudies-literature

Inside polyMOFs: layered structures in polymer-based metal-organic frameworks.

Project description:In this report, we explore the internal structural features of polyMOFs consisting of equal mass ratios of metal-coordinating poly(benzenedicarboxylic acid) blocks and non-coordinating poly(ethylene glycol) (PEG) blocks. The studies reveal alternating lamellae of metal-rich, crystalline regions and metal-deficient non-crystalline polymer, which span the length of hundreds of nanometers. Polymers consisting of random PEG blocks, PEG end-blocks, or non-coordinating poly(cyclooctadiene) (COD) show similar alternation of metal-rich and metal-deficient regions, indicating a universal self-assembly mechanism. A variety of techniques were employed to interrogate the internal structure of the polyMOFs, including transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and small-angle synchrotron X-ray scattering (SAXS). Independent of the copolymer architecture or composition, the internal structure of the polyMOF crystals showed similar lamellar self-assembly at single-nanometer length scales.

| S-EPMC8162296 | biostudies-literature

Exchange Bias in a Layered Metal-Organic Topological Spin Glass.

Project description:The discovery of conductive and magnetic two-dimensional (2D) materials is critical for the development of next generation spintronics devices. Coordination chemistry in particular represents a highly versatile, though underutilized, route toward the synthesis of such materials with designer lattices. Here, we report the synthesis of a conductive, layered 2D metal-organic kagome lattice, Mn3(C6S6), using mild solution-phase chemistry. Strong geometric spin frustration in this system mediates spin freezing at low temperatures, which results in glassy magnetic dynamics consistent with a rare geometrically frustrated (topological) spin glass. Notably, we show that this geometric frustration engenders a large, tunable exchange bias of 1625 Oe in Mn3(C6S6), providing the first example of exchange bias in a coordination solid or a topological spin glass. Exchange bias is a critical component in a number of spintronics applications, but it is difficult to rationally tune, as it typically arises due to structural disorder. This work outlines a new strategy for engineering exchange bias systems using single-phase, crystalline lattices. More generally, these results demonstrate the potential utility of geometric frustration in the design of new nanoscale spintronic materials.

| S-EPMC8483270 | biostudies-literature

Reversible switching of arylazopyrazole within a metal-organic cage.

Project description:Arylazopyrazoles represent a new family of molecular photoswitches characterized by a near-quantitative conversion between two states and long thermal half-lives of the metastable state. Here, we investigated the behavior of a model arylazopyrazole in the presence of a self-assembled cage based on Pd-imidazole coordination. Owing to its high water solubility, the cage can solubilize the E isomer of arylazopyrazole, which, by itself, is not soluble in water. NMR spectroscopy and X-ray crystallography have independently demonstrated that each cage can encapsulate two molecules of E-arylazopyrazole. UV-induced switching to the Z isomer was accompanied by the release of one of the two guests from the cage and the formation of a 1:1 cage/Z-arylazopyrazole inclusion complex. DFT calculations suggest that this process involves a dramatic change in the conformation of the cage. Back-isomerization was induced with green light and resulted in the initial 1:2 cage/E-arylazopyrazole complex. This back-isomerization reaction also proceeded in the dark, with a rate significantly higher than in the absence of the cage.

| S-EPMC6808206 | 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