A Photosensitizing Metal–Organic Framework as a Tandem Reaction Catalyst for Primary Alcohols from Terminal Alkenes and Alkynes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(35)

Опубликована: Июнь 1, 2023

Owing to the wide and growing demand for primary alcohols, development of efficient catalysts with high regioselectivity remains a worthwhile pursuit. However, according Markovnikov's rule, it is challenge obtain alcohols yields from terminal alkenes or alkynes. Herein, we report synthesis photosensitizing two-dimensional (2D) metal-organic framework (MOF) cyclic trinuclear copper(I) units (Cu-CTUs) boron dipyrro-methene (Bodipy) ligand. The MOF features broadband light absorption, excellent photoinduced charge separation efficiency, photochemical properties. By integrating copper-catalyzed hydroboration photocatalyzed aerobic oxidation, can catalyze alkynes produce via one-pot tandem reaction regioselectivity, good overall in two-step reactions (up 85 %), broad substrate compatibility (32 examples) reusability under mild conditions.

Язык: Английский

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Post‐Nickelation of a Crystalline Trinuclear Copper Organic Framework for Synergistic Photocatalytic Carbon Dioxide Conversion

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(18)

Опубликована: Март 9, 2023

Rational regulation of electronic structures and functionalities framework materials still remains challenging. Herein, reaction 4,4',4''-nitrilo-tribenzhydrazide with tris(μ2 -4-carboxaldehyde-pyrazolato-N,N')-tricopper (Cu3 Py3 ) generates the crystalline copper organic USTB-11(Cu). Post-modification divalent nickel ions affords heterometallic USTB-11(Cu,Ni). Powder X-ray diffraction theoretical simulations reveal their two-dimensional hexagonal structure geometry. A series advanced spectroscopic techniques disclose mixed CuI /CuII state nature Cu3 in USTB-11(Cu,Ni) a uniform bistable Cu34+ (CuI2 CuII : Cu35+ (CuI CuII2 (ca. 1 3) oxidation state, resulting significantly improved formation efficiency charge-separation state. This endows Ni sites enhanced activity outstanding photocatalytic CO2 to CO performance conversion rate 22 130 μmol g-1 h-1 selectivity 98 %.

Язык: Английский

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Gold(I)-Organic Frameworks as Catalysts for Carboxylation of Alkynes with CO₂

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(41), С. 22720 - 22727

Опубликована: Окт. 4, 2023

Construction of gold-based metal-organic frameworks (Au-MOFs) would bring the merits gold chemistry into MOFs. However, it still remains challenging because cations are easily reduced to metallic under solvothermal conditions. Herein, we present first example Au-MOFs prepared from networking cyclic trinuclear gold(I) complexes by formal transimination reaction in a rapid (<15 min) and scalable (up 1 g) fashion ambient condition. The feature uniform porosity, high crystallinity, superior chemical stability toward base (i.e., 20 M NaOH). With open Au(I) sites skeleton, as heterogeneous catalysts delivered good performance substrate tolerance for carboxylation reactions alkynes with CO2. This work demonstrates facile approach reticularly synthesize combining coordination dynamic covalent chemistry.

Язык: Английский

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Molecular Engineering of Metal–Organic Layers for Sustainable Tandem and Synergistic Photocatalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(7), С. 4158 - 4165

Опубликована: Фев. 8, 2023

Metal–organic layers (MOLs), a monolayered version of metal–organic frameworks (MOFs), have recently emerged as novel two-dimensional molecular material platform to design multifunctional catalysts. MOLs inherit the intrinsic tunability MOFs and yet more accessible modifiable building blocks. Here we report engineering six via modulated solvothermal synthesis between HfCl4 three photosensitizing ligands followed by postsynthetic modification with two carboxylate-containing cobaloximes for tandem synergistic photocatalysis. Morphological structural characterization transmission electron microscopy atomic force compositional analysis inductively coupled plasma-mass spectrometry nuclear magnetic resonance spectroscopy establish flat nanoplates periodic lattice structure hexagonal symmetry. The efficiently catalyze dehydrogenative coupling reactions Heck-type reactions. most active MOL catalyst was used gram-scale vesnarinone, cardiotonic agent, in 80% yield turnover number 400 eight consecutive reaction cycles without significant loss activities.

Язык: Английский

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Coordination directed metal covalent organic frameworks

Materials Chemistry Frontiers, Год журнала: 2023, Номер 7(15), С. 2995 - 3010

Опубликована: Янв. 1, 2023

The research on coordination directed metal covalent organic frameworks (MCOFs) is systematically reviewed for the continued development of this emerging field.

Язык: Английский

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Tailoring stability, catalytic activity and selectivity of covalent metal–organic frameworks via steric modification of metal nodes

Journal of Materials Chemistry A, Год журнала: 2023, Номер 11(24), С. 12777 - 12783

Опубликована: Янв. 1, 2023

A novel and efficient strategy was developed to enhance the stability, control catalytic activity, improve selectivity of Cu( i ) cyclic trinuclear unit (Cu-CTU)-based metal–organic frameworks by steric modification copper nodes.

Язык: Английский

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Recent advances in bimetallic metal-organic frameworks and their derivatives for thermal catalysis

Nano Research, Год журнала: 2023, Номер 16(12), С. 12919 - 12935

Опубликована: Авг. 8, 2023

Язык: Английский

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Heterovalent Metal Pair Sites on Metal–Organic Framework Ordered Macropores for Multimolecular Co-Activation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(12), С. 8425 - 8434

Опубликована: Март 15, 2024

The precise design of catalytic metal centers with multiple chemical states to facilitate sophisticated reactions involving multimolecular activation is highly desirable but challenging. Herein, we report an ordered macroporous catalyst heterovalent pair (HMP) sites comprising CuII–CuI on the basis a microporous metal–organic framework (MOF) system. This HMP proximity dual copper sites, whose distance controlled ∼2.6 Å, macropore surface exhibits co-activation behavior ethanol at CuII and alkyne CuI, avoids restriction, thereby promoting additive-free hydroboration reaction. desired yield enhances dramatically compared pristine MOF both solely isovalent CuII–CuII sites. Density functional theory calculations reveal that Cu-HMP can stabilize Bpin-CuII–CuI-alkyne intermediate C–B bond formation, resulting in smooth process. work provides new perspectives catalysts for matter transformations.

Язык: Английский

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Constructing molecular junction in covalent organic frameworks for efficient uranium(VI) photoreduction

Applied Catalysis B Environment and Energy, Год журнала: 2024, Номер 352, С. 124053 - 124053

Опубликована: Апрель 21, 2024

Язык: Английский

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Functional Regulation of Covalent Organic Frameworks for Photocatalytic Water Splitting

ACS Materials Letters, Год журнала: 2024, Номер 6(6), С. 2276 - 2294

Опубликована: Май 10, 2024

Solar-driven water splitting into hydrogen and oxygen fuels represents a promising way for clean energy production to achieve carbon-neutral future. The efficiency of photocatalytic strongly relies on the development high-performance catalysts. Noteworthily, covalent organic frameworks (COFs) offer distinctive platform designing photo-to-chemical conversion, benefiting from their tailorable structure, ultrahigh porosity, robust framework, sufficient light absorption, rich active sites. Herein we highlight systematic overview recent research progress using COFs half-reactions overall splitting. With an aim shed understanding structural design COF photocatalysts splitting, various functional strategies are discussed. Finally, major challenges future perspectives proposed with hope achieving ongoing this emerging field.

Язык: Английский

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