Flexible Metal–Organic Frameworks: From Local Structural Design to Functional Realization

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(16), P. 2279 - 2292

Published: Aug. 8, 2024

ConspectusFlexible metal–organic frameworks (MOFs), also known as soft porous crystals, exhibit dynamic behaviors in response to external physical and chemical stimuli such light, heat, electric or magnetic field, the presence of particular matters, on premise maintaining their crystalline state. The reversible structural transformation flexible MOFs, a unique characteristic seldomly found other types solid-state materials, affords them distinct properties realms molecule separation, optoelectronic devices, sensing, information storage, biomedicine applications, so on. mechanisms underlying can be comprehensively investigated at molecular level by means situ single-crystal powder X-ray diffraction well spectroscopic techniques due high regularity these materials during stimuli-responsive phase transitions. Through introduction specific groups/moieties into well-defined ordered arrays, targeted applications achieved, performance MOFs further improved via rational design.In this Account, we summarize our progress design, synthesis, over past few years. First, highlight construction principle emphasizing pivotal role local design. Using an F-modified ligand, MOF with remarkable transformations obtained; regulation metal coordination environment interpenetrating is crucial for achieving MOFs. We propose strong correlation strategy based supramolecular interactions between guest molecules framework, which realizes temperature-responsive spatial "open-closed" regulation. Mechanisms were presented obtained materials. Second, some representative newly developed systems reviewed. gas responsive show efficient short-chain alkane separation discriminatory sorption behavior toward similar gaseous substrates. Smart sensing temperature, pressure, volatile organic compounds was achieved several novel fluorescent optimization potential through state-of-the-art Furthermore, multiferroic multiple bistable states working temperatures MOFs.Finally, provide discussion challenges future research, including precise in-depth structure–property relationship investigation, optimization, industrialization. hope that Account will stimulate research interest developing next-generation smart challenging extreme environmental massive beyond.

Language: Английский

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Photoswitchable Catalysis by a Self-Assembled Molecular Cage

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21196 - 21202

Published: July 25, 2024

A heteroleptic [Pd

Language: Английский

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Cooperative and Orthogonal Switching in the Solid State Enabled by Metal‐Organic Framework Confinement Leading to a Thermo‐Photochromic Platform

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(37)

Published: July 24, 2023

Cooperative behavior and orthogonal responses of two classes coordinatively integrated photochromic molecules towards distinct external stimuli were demonstrated on the first example a photo-thermo-responsive hierarchical platform. Synergetic to temperature excitation wavelength are achieved by confining stimuli-responsive moieties within metal-organic framework (MOF), leading preparation novel spiropyran-diarylethene based material. Synergistic photoswitches enables study resonance energy transfer as well control photoinduced charge processes, milestones required advance optoelectronics development. Spectroscopic studies in combination with theoretical modeling revealed nonlinear effect material electronic structure arising from coordinative integration photoresponsive photoisomerization mechanisms. Thus, reported work covers multivariable facets not only fundamental aspects photoswitch cooperativity, but also provides pathway modulate photophysics electronics multidimensional functional materials exhibiting thermo-photochromism.

Language: Английский

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Macrocyclic ligand-driven ion selectivity and high surface area in a 2D conductive MOF

Chem, Journal Year: 2023, Volume and Issue: 10(1), P. 199 - 210

Published: Sept. 22, 2023

Language: Английский

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Maximizing the Potential of Electrically Conductive MOFs

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 31, 2024

ConspectusElectrically conductive metal–organic frameworks (EC-MOFs) have emerged as a compelling class of materials, drawing increasing attention due to their unique properties facilitating charge transport within porous structures. The synergy between electrical conductivity and porosity has opened wide range applications, including electrocatalysis, energy storage, chemiresistive sensing, electronic devices that been underexplored for insulating counterparts. Despite these promising prospects, prevalent challenge arises from the predominant adoption two-dimensional (2D) structures by most EC-MOFs. These 2D often show modest surface areas short interlayer distances, hindering molecular accessibility, which deviates inherent characteristics conventional MOFs. Furthermore, quest efficient imposes design constraints, leading restricted selection functional building blocks. Additionally, there is lack established functionalization methods EC-MOFs, limiting diversity. Thus, challenges impeded EC-MOFs reaching full potential.In this Account, we summarize discuss our group's efforts aimed at enhancing accessibility deploying diversity Our focus on involves several strategies. First, employed macrocyclic ligands with intrinsic pockets blocks integrated in supplement additional pores enhance accessibility. resulting ligand-based exhibit exceptionally high confer advantages electrochemical performances. Second, extend addressing structural limitations, frequently associated EC-MOFs' Through pillar insertion strategy, transformed EC-MOF platform into three-dimensional (3D) structure, thereby achieving higher enhanced In pursuing diversity, delved molecular-level tuning We demonstrated electron-rich alkyne-based can host transition metals alkali ions, enabling ion selectivity showcasing diverse use utilized postsynthetic approach further functionalize metal nodes level an framework, introducing proton-conducting pathway while preserving its conductivity.We aspire Account provide practical insights strategies surmount limitations realm By integrating functionality, endeavor propel utility materials will inspire rational development future unlock potential.

Language: Английский

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Azobenzene-Integrated NHC Ligands: A Versatile Platform for Visible-Light-Switchable Metal Catalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(19), P. 13210 - 13225

Published: May 6, 2024

A new class of photoswitchable NHC ligands, named azImBA, has been developed by integrating azobenzene into a previously unreported imidazobenzoxazol-1-ylidene framework. These rigid photochromic carbenes enable precise control over confinement around metal's coordination sphere. As model system, gold(I) complexes these NHCs exhibit efficient bidirectional E–Z isomerization under visible light, offering versatile platform for reversibly photomodulating the reactivity organogold species. Comprehensive kinetic studies protodeauration reaction reveal rate differences up to 2 orders magnitude between E and Z isomers NHCs, resulting in quasi-complete visible-light-gated ON/OFF switchable system. Such high level photomodulation efficiency is unprecedented gold complexes, challenging current state-of-the-art organometallics. Thorough investigations ligand properties paired with structure–reactivity correlations underscored unique ligand's steric features as key factor reactivity. This effective photocontrol strategy was further validated catalysis, enabling situ photoswitching catalytic activity intramolecular hydroalkoxylation -amination alkynes. Given significance findings its potential widely applicable, easily customizable ancillary platform, azImBA poised stimulate development adaptive, multifunctional metal complexes.

Language: Английский

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Switching from Molecules to Functional Materials: Breakthroughs in Photochromism With MOFs

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 7, 2024

Abstract Photochromic materials with properties that can be dynamically tailored as a function of external stimuli are rapidly expanding field driven by applications in areas ranging from molecular computing, nanotechnology, or photopharmacology to programable heterogeneous catalysis. Challenges arise, however, when translating the rapid, solution‐like response stimuli‐responsive moieties solid‐state due intermolecular interactions imposed through close packing bulk solids. As result, integration photochromic compounds into synthetically porous matrices, such metal‐organic frameworks (MOFs), has come forefront an emerging strategy for material development. This review highlights how core principles reticular chemistry (on example MOFs) play critical role performance, surpassing limitations previously observed solution solid state. The symbiotic relationship between photoresponsive and focus on synthesis creates avenues toward tailorable photoisomerization kinetics, directional energy charge transfer, switchable gas sorption, synergistic chromophore communication is discussed. not only focuses recent cutting‐edge advancements development, but also novel, vital‐to‐pursue pathways multifaceted functional realms energy, technology, biomedicine.

Language: Английский

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Switching in harmony: Tailoring the properties of functional materials with orthogonal stimuli

Chemical Physics Reviews, Journal Year: 2024, Volume and Issue: 5(1)

Published: Feb. 1, 2024

Bridging the current gap between precision and efficiency demonstrated by natural systems synthetic materials requires interfacing independently controlling multiple stimuli-responsive building blocks in a single platform. The mentioned orthogonal control over material properties (i.e., ability to selectively activate one moiety without affecting another) could pave way for multitude of applications, including logic-gated optoelectronics, on-demand drug delivery platforms, molecular shuttles, example. In this Review, we highlight recent successful strategies achieve using combination independent stimuli. We begin surveying fundamental studies multi-stimuli-responsive systems, which utilize variety stimuli (e.g., spiropyran, diarylethene, or dihydroazulene derivatives), because these lay foundation design containing more than controlled fragment. As next step, overview emerging field focusing on are composed unique unit that can respond stimuli, distinct excitation wavelengths, light, heat, pH, potential, ionic strength. Recent advances clearly demonstrate how strategic coupling orthogonally units allow selective modulation range properties, such as conductivity, catalytic performance, biological activity. Thus, highlighted foreshadow role with impact generation photopharmacology, nanotechnology, biomimetics.

Language: Английский

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Dissolution‐Recrystallization: A Novel Mechanism for Fluorochromic Detection of Th⁴⁺ Using Color‐Tunable Luminescent Metal–Organic Frameworks

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: July 22, 2024

Thorium, a predominant actinide in the Earth's crust, presents significant environmental and health risks due to its radioactive nature. These are particularly pronounced during mining processing of monazite for rare earth elements (REEs), which contain substantial thorium concentrations. Current instrumental analysis methods thorium, offer high accuracy but require laborious sample preparations expensive instruments, making them unsuitable on-site analysis. Herein, we present class color-tunable luminescent lanthanide-based metal-organic frameworks (Ln-MOFs) as fluorochromic sensors Th

Language: Английский

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Artificial molecular machines: Design and observation

Smart Molecules, Journal Year: 2023, Volume and Issue: 1(3)

Published: Oct. 23, 2023

Abstract Natural molecular machines have inspired the development of artificial machines, which potential to revolutionize several areas technology. Artificial commonly employ switches, motors, and shuttles as fundamental building blocks. The observation constructed by these blocks can be highly challenging due their small sizes intricate behaviors. use modern instrumentation advanced observational techniques plays a crucial role in characterization machines. Furthermore, well‐designed structure is also critical factor making more observable. This review summarizes common methods from diverse perspectives used observe emphasizes significance comprehending behaviors design superior

Language: Английский

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