Copper Atom Pairs Stabilize *OCCO Dipole Toward Highly Selective CO2 Electroreduction to C2H4

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(50)

Опубликована: Авг. 13, 2024

Abstract Deeply electrolytic reduction of carbon dioxide (CO 2 ) to high‐value ethylene (C H 4 is very attractive. However, the sluggish kinetics C−C coupling seriously results in low selectivity CO electroreduction C . Herein, we report a copper‐based polyhedron (Cu2) that features uniformly distributed and atomically precise bi‐Cu units, which can stabilize *OCCO dipole facilitate for high selective production. The faradaic efficiency (FE) reaches 51 % with current density 469.4 mA cm −2 , much superior Cu single site catalyst (Cu SAC) (~0 %). Moreover, Cu2 has higher turnover frequency (TOF, ~520 h −1 compared nanoparticles (~9.42 SAC (~0.87 ). In situ characterizations theoretical calculations revealed unique structural configuration could optimize moments adsorbate promote generation

Язык: Английский

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Metallacycles, metallacages, and their aggregate/optical behavior

Aggregate, Год журнала: 2021, Номер 2(5)

Опубликована: Июнь 24, 2021

Abstract Since the first metallacycle was prepared by Verkade in 1983, various metallacycles and metallacages with controllable nanoscale shapes sizes have been created modular design synthesis, showing unique properties that enable applications catalysis, sensors, biomedicine. Everything from their photophysical to antitumor activities catalysis found be influenced suprastructures. Thus, it is necessary helpful develop a systematic understanding of relationships among micro/nanostructures, resultant photophysical/chemical properties, corresponding applications. In this review, we summarized latest progress area approximately past 5 years.

Язык: Английский

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An Adaptable Water-Soluble Molecular Boat for Selective Separation of Phenanthrene from Isomeric Anthracene

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(16), С. 7504 - 7513

Опубликована: Апрель 18, 2022

Anthracene crude oil is a common source of phenanthrene for its industrial use. The isolation from this challenging task due to very similar physical properties isomer anthracene. We report here water-soluble Pd(II) molecular boat (MB1) with unusual structural topology that was obtained by assembling flexible tetrapyridyl donor (L) cis-Pd(II) acceptor. backbone the enabled it breathe in presence guest optimizing fit within cavity. binds more strongly than anthracene, which separation an >98% purity equimolar mixture two isomers using MB1 as extracting agent. represents unique example coordination receptor suitable selective aqueous extraction anthracene reusability several cycles.

Язык: Английский

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Chiral Carbon Nanorings: Synthesis, Properties and Hierarchical Self‐assembly of Chiral Ternary Complexes Featuring a Narcissistic Chiral Self‐Recognition for Chiral Amines

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(28)

Опубликована: Май 17, 2023

We report the synthesis and chiroptical properties of novel chiral carbon nanorings Sp-/Rp-[12]PCPP containing a planar [2.2]PCP unit, demonstrate that can not only host crown ether 18-Crown-6 to form ring-in-ring complexes with binding constant 3.35×103 M-1 , but also accommodate S/R-protonated amines homochiral S@Sp-/R@Rp- heterochiral S@Rp-/R@Sp- ternary complexes, displaying significantly larger constants up 3.31×105 depending on guests. Importantly, exhibit an enhanced CD signal, while ones have signal compared nanorings, respectively, which suggests display highly narcissistic self-recognition for amines, respectively. Finally, be further applied determine ee values The findings highlight new application in supramolecular sensors, beyond common recognition π-conjugated molecules.

Язык: Английский

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Encapsulating Semiconductor Quantum Dots in Supramolecular Cages Enables Ultrafast Guest–Host Electron and Vibrational Energy Transfer

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(9), С. 5191 - 5202

Опубликована: Фев. 6, 2023

In the field of supramolecular chemistry, host-guest systems have been extensively explored to encapsulate a wide range substrates, owing emerging functionalities in nanoconfined space that cannot be achieved dilute solutions. However, chemistry is still limited encapsulation small guests. Herein, we construct water-soluble metallo-supramolecular hexagonal prism with large hydrophobic cavity by anchoring multiple polyethylene glycol chains onto building blocks. Then, assembled prisms are able quantum dots (QDs) diameters less than 5.0 nm. Furthermore, find cage around each QD strongly modifies photophysics universally increasing rates relaxation processes via ultrafast electron and vibrational energy transfer. Taken together, these efforts expand scope substrates provide new approach tune optical properties QDs.

Язык: Английский

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Combining Multiple Photosensitizer Modules into One Supramolecular System for Synergetic Enhanced Photodynamic Therapy

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(11)

Опубликована: Янв. 9, 2024

Photodynamic therapy (PDT), as an emerging cancer treatment, requires the development of highly desirable photosensitizers (PSs) with integrated functional groups to achieve enhanced therapeutic efficacy. Coordination-driven self-assembly (CDSA) would provide alternative approach for combining multiple PSs synergistically. Here, we demonstrate a simple yet powerful strategy conventional chromophores (tetraphenylethylene, porphyrin, or Zn-porphyrin) pyridinium salt together through condensation reactions, followed by CDSA construct series novel metallo-supramolecular (S1-S3). The generation reactive oxygen species (ROS) is dramatically direct combination two different PSs, and further reinforced in subsequent ensembles. Among all ensembles, S2 porphyrin cores shows highest ROS efficiency, specific interactions lysosome, strong emission probing cells. Moreover, cellular living experiments confirm that has excellent PDT efficacy, biocompatibility, biosafety. As such, this study will enable more efficient potential clinical applications.

Язык: Английский

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Unraveling the photo-induced dynamic behavior of COF-based Z-scheme heterostructure monolithic aerogels

Matter, Год журнала: 2024, Номер 7(9), С. 3145 - 3162

Опубликована: Май 23, 2024

Язык: Английский

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Multidimensional Mass Spectrometry Assisted Metallo-Supramolecular Chemistry

CCS Chemistry, Год журнала: 2021, Номер 4(3), С. 785 - 808

Опубликована: Окт. 12, 2021

Open AccessCCS ChemistryMINI REVIEW1 Mar 2022Multidimensional Mass Spectrometry Assisted Metallo-Supramolecular Chemistry Heng Wang, Chenxing Guo and Xiaopeng Li Wang College of Environmental Engineering, Shenzhen University, 518073 University General Hospital, Clinical Medical Academy, 518055 , *Corresponding author: E-mail Address: [email protected] https://doi.org/10.31635/ccschem.021.202101408 SectionsAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Metallo-supramolecular chemistry based on the reversible, directional, predictable noncovalent interaction metal–ligand coordination has been widely applied in constructing a myriad two- three-dimensional supramolecules with sophisticated structures. The development metallo-supramolecular highly relies facile characterization methods. For advancement structural complexity desired functions, however, conventional crystallographic spectroscopic characterizations are limited by crystal growth, sample purity, severe signal overlaps. With high sensitivity low requirement for multidimensional mass spectrometry (MS), including electrospray ionization-MS (ESI-MS), tandem MS (MS2), ion mobility-MS (IM-MS), is emerging as an essential analytical tool chemical compositions, connectivity, stability, shape, size metallo-supramolecules, well kinetic thermodynamic features self-assembly processes. Thus, this review mainly focuses recent discusses how ESI-MS, MS2, IM-MS assist chemistry. Download figure PowerPoint Introduction Supramolecular self-assembly, inspired precise organization bio-macromolecules living systems, allows spontaneous formation ordered complexes from chaos state.1 Among various driving forces, plays vital role structurally functionally benefitting directionality feature bonds.2–6 As result, witnessed explosion artificial supramolecular architectures, polygons,7–11 knots,12–15 links,16–19 fractals,20–22 Platonic,23–27 Archimedean,28–34 Goldenberg polyhedrons,35,36 so on. And these show great potentials among different fields, catalysis,37–46 nano-electronics,47,48 stabilization air- or water-sensitive molecules,49–51 disease diagnosis therapy,52–57 Furthermore, delicate assembling approaches, inter alia, directional bonding,2 symmetry interactions,58 molecular paneling,59 sub-components,60 have developed exploration Compared flourish strategies, lack efficient methods always limits investigation assembled at equilibrium details processes solution because weak dynamic nature metallo-supramolecules. single-crystal X-ray diffraction (SC-XRD) powerful direct method that detailed information atomic level.61 However, it remains formidable challenge obtain high-quality single crystals, particularly metallo-supramolecules large voids filled disordered solvent molecules counterions. In addition, refinement structures difficult current approaches were small molecules. Apart those issues obtained through SC-XRD solid phase may not correlate study systems gas phase. Another well-established NMR spectroscopy, whereby nuclei such 1H, 13C, 19F, 31P, can be detected, allowing environment elucidated.62,63 Through two-dimensional (2D) techniques, example, 1H–1H correlation spectroscopy (COSY), nuclear Overhauser effect (NOESY), diffusion (DOSY), diverse about further obtained, coordinations, geometric distributions nuclei, shape architectures. application also analyzing samples overlapping signals, containing paramagnetic metal ions. complementary microscopic methods, force microscopy (AFM), scanning tunneling (STM), transmission electron (TEM), directly image analytes. AFM STM, which tips probe surface target substrates, reveal individual molecule64 distinguish ions using (STS).65 resolution sharp tips, without impurities, aggregations, dissociations supramolecules. TEM uses electrons "probe" offer entire structure assisted computer-assisted (3D) reconstruction, selected area (SAED), energy dispersive (EDX) techniques.66 Unfortunately, addition challenges preparing sample, suffers intrinsic instability under beam during preparation. mass-to-charge ratio (m/z) intact (MS) measurements enables determination composition provides higher but lower purity than analysis NMR. Such along speed make possible monitor process before system question reaches equilibrium. determining monitoring reaction traditional suffer fragmentation bound even when soft ionization method, is, (ESI), applied. Cold-spray (CSI),67 equipped ESI source cooled liquid nitrogen, was used overcome problem lowering internal gained ionization. Due labile matrix-assisted laser desorption/ionization (MALDI) could cause very thus preferred m/z MS, (MS2) (IM-MS) elucidate more First, controllable technique, MS2 offers deeper insight into analytes, stability connectivity orthogonal situ separation identify species same m/z; importantly, terms During past two decades, combination IM-MS, played important Here, we discuss (1) (2) distinguishing isomers by-products present combinatorial library, (3) investigating More anticipate would only act serve design next-generation advance new synthetic strategies. ESI-MS Studies Charged ideal analytes studies easy-to-ionize counterions readily stripped off, especially polar volatile solvents. advantage its capability reducing signals corresponding multiply charged molar (<104 Da) range analyzers, since measures values ensembles. Consequently, series peaks usually observed, representing charge states analyte successive loss To minimize ionization, crucial ionize fragile mild conditions, careful selection focusing voltages, operation temperature, fast extraction increasing pressure (or vacuum).68 Additionally, concentrated often required inhibit potential entropy-driven dissociation solution, although needs extensive cleaning after each measurement. Without annoying fragmentation, suitable detecting compositions ionic providing regarding following aspects self-assembly: screening structures; self-assembly; minor products guide design. Acting fast-screening approach Fast analytes' does require purification otherwise inevitable measurement growth. most cases, simply removing inorganic salts reduce suppression, resulting ready control stoichiometry, self-assembled subjected any purification. multiple assemblies numbers building blocks, host–guest adducts. Therefore, superior perform compared first example showcasing generations metallo-dendrimers S1/ S2 (Figure 1a) comprised polyazaaromatic Ru(II) reported Kirsch-De Mesmaeker et al.69 generated clear simple patterns allowed unambiguous formula, whereas other just provided nonconclusive data 1b). Second, metallo-macrocycles Newkome co-workers,701H gave similar shifts hexagon, octagon, decagon ( S3- S5) Ru(II)-connected bitopic 2,2′:6′,2″-terpyridyl (TPY) subunit L3 1c) environments detected protons. contrast, analogs distinct unambiguously identified where three sets (Figures 1d 1e).70 Figure 1 | acting preparation (a b) spectrum; (c–e) TPY-Ru(II)/Fe(II)-based metallo-hexagon S3, -octagon S4, -decagon S5 1H spectra spectra; (f–h) fractals S6 complexation between TPY-based ligand spectrum Co(II) complex (S6-Co). Adapted permission ref 69. Copyright 1996 American Chemical Society. 70. 2011 Wiley-VCH. 71. 2020 Metallo-supramolecules transition unpaired remain characterization. no characterizing samples. Shionoya al.25 constructed octahedra mixing tritopic pyridinyl block Cu(II), Ni(II), Co(II), Mn(II) clearly showed dominant set ascribed designed whereas, displayed broad information.25 Similarly, help characterization, coordination-driven TPY-paramagnetic construct al.,71 expanded library architectures up platform studying 1f–1h). When Ni(II) cages sub-component strategy, reliable identifying structures.72,73 Investigation subfield chemistry, related fundamental recognition applications metal–organic containers. extensively provide evidence diagnostic protons guest cannot accurately address many encapsulated properly examine exact change upon encapsulation molecules, thus, accurate value deducing number M8L6 (M = ion, L ligand) cube porphyrin faces, Nitschke al.74 described guests coronene fullerene selectively 2a). complicated 2:1 environments, coronene-encapsulated via deconvolution 2b 2c). confirmed selective C70, C76, C82, C84 over C60 soot, evidenced absence discernible assignable C60-encapsulated guest-free cube. 2 ESI-MS-based cages. (a–c) Self-assembly porphyrin-faced S8 ESI-MS; (d e) PBI-edged tetrahedron capable encapsulating C60S9 peanut S10 simultaneous one diamantane phenanthrenes (S11) ESI-MS. 74. 76. 2013 83. 2017 Springer Nature. feasible rapid qualitatively selectivity certain metallo-supramolecule guests. another encapsulation, tetragonal prism mixture derivatives, determined comparing relative abundance them, PCBM-C60 affinity host N-methylpyrrolidine-C60.75 still challenging quantitatively determine efficiency complexes, same. Ideally, quantitative if efficiencies calibrated. molecule, Würthner al.76 unequivocally prove inside cavity perylene-bisimide (PBI) edged S9 2d 2e). Note bear 13C Although confirm C60, unable allow opposed trigonal prisms, wherein C3-symmetrical pyridyl ligands, linear ditopic end-capped Pd(II) moiety served base pillars, vertices, respectively, found excellent container variety including, coronene,77 triphenylene,78 pyrene-4,5-dione,79,80 complexes.81,82 intriguingly, precisely manipulated tuning length organic pillars. A situation Yoshizawa al.83 heteroleptically types guests, phenanthrenes, cavities 2f). result 2g), unusual 2h), expected found. Monitoring unveiling bonded interactions exhibit due reassociation bonds. hard investigate techniques solution. Nevertheless, measurement, separated "frozen" display instead system. type process, exchange involves disassociation supramolecule subsequent replacement ligand. bond strength activation energies If time scales exchanges comparable should able kinds pre-assembled masses ligands MS. Once occurs, re-assembled initial ensembles different, all specifically recorded Fujita al.84 M12L24 spheres topologically identical bearing alkyl chains (–OC3H7 vs –OC6H13) then time-dependent 3a 3b). difference mass, exchanged ones easily spectra. Time-dependent revealed quite remarkable exchange. half-time measured approximately 20 days. After evaluating spherical supramolecules, estimated rate × 10−2 M−1·s−1, far less free sphere (half-time 23 min). semi-quantitatively fully closed framework slowed down cooperative effect.84 utilized carefully metallo-polygons organoplatinum motifs 1H/2D isotope labeling.85 rates, understanding depended experimental conditions solvent, 3 (a) Ligand (Pd12L724 Pd12L824) chain lengths (-n-C3H7 -n-C6H13), (b) (c) four snowflakes (S12–S15) arm (d) S12/S13 (e) S12/S15. 84. 2009 (c Reprinted 88. 2019 87. system, profound TPY.71,86–88 By assigned hybrid spectra, had degree tolerance variation adjusting conformation forming ensembles.28–30 arms (ΔI). ΔI, smaller faster ΔI 0.28 nm, reached within 5 days;87 0.54 nm 7 days reaching equilibrium, 0.97 resulted 3c–3e).88 hexagonal fractals. evaluate seven M(II) Mn, Fe, Co, Ni, Cu, Zn, Cd) Each divalent assemble masses. pair collect structure. calibrating rates 298 K sequence Cd(II) < ≈ Cu(II) Zn(II) << Fe(II)- Ni(II)-based too inert enable highest Cd(II)-based 2.9 103 1012 times Co(II)-based (1.7 10−9 M−1·s−1).71 intermediates existing studied tris-bipyridine Fe(II) ions, gradual indicating existence intermediate circular helicate.89 did intermediates. track transformation successfully capture intermediate, helicate, proving ion. mechanism process. Kandinsky circle synthesis achieved "one-pot" fashion. results strongly suggested orthogonality condensation 4a 4b).90 4 S16 one-pot process; transformation. 90. species, revealed, thereby mechanisms. instance, assembly multi-layered TPY form ring-in-ring spiderweb structures, settled rim longer shorter arms, observed gradually ratios.91 observation intramolecular occurred prior intermolecular assembly. preference some captured suggesting generality.92 Also, analyses pentatopic self-assembly. state preferential faces concentric hexagon discovery guided serving roles, lateral edges, giant prism.93 Detecting unexpected facilitate values, assemblies, carrying out time- effort-consuming bonding approach, adamantane-based 3D Cd(II).94 According classic polyhedra, structure(s) triangular bipyramidal, tetrahedral, cubical, dodecahedral. failed poor solubility. strong cube, encouraged modification enhance solubility full determination.94 Based

Язык: Английский

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A novel metal–organic complex surfactant for high-efficiency mineral flotation

Chemical Engineering Journal, Год журнала: 2021, Номер 426, С. 130853 - 130853

Опубликована: Июнь 16, 2021

Язык: Английский

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Synthesis of Planet‐Like Liquid Metal Nanodroplets with Promising Properties for Catalysis

Advanced Functional Materials, Год журнала: 2023, Номер 34(31)

Опубликована: Июль 12, 2023

Abstract Liquid metal nanodroplets are an emerging class of underexplored materials with significant potential in many applications, including catalysis, bio‐therapeutics, and phase‐change materials. These nanostructures generally synthesized by mechanical agitation via ultrasonication low‐melting metals like Ga. Once these successfully synthesized, they can be suspended a vast array different solvents. However, one major issue arises specifically liquid alloys which found to de‐alloy the sonication process. Here, it is demonstrated that this challenge overcome undertaking at high temperatures, suspending within molten sodium acetate (NaOAc). After cooling, become planet‐like covered interfacial oxide crust, feature mantle, solid core. The salt solvent effectively removed rendering approach ideal, especially for catalysts. proof‐of‐concept application carrying out electrocatalytic ethanol oxidation, using Cu–Ga system. superior performance highlights catalyzing reactions. Aside from system, facile process applied multiple other systems, Ag–Ga, Zn–Ga, Bi–Ga, In–Cu, Sn–Cu.

Язык: Английский

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