Light-Induced Polymeric Frustrated Radical Pairs as Building Blocks for Materials and Photocatalysts DOI Creative Commons
Meng Wang, Muralidharan Shanmugam, Eric J. L. McInnes

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(44), P. 24294 - 24301

Published: Oct. 27, 2023

Polymeric frustrated Lewis pairs, or poly(FLP)s, have served to bridge the gap between functional polymer science and main group catalysis, pairing uniqueness of sterically acids bases with a scaffold create self-healing gels recyclable catalysts. However, their utilization in radical chemistry is unprecedented. In this paper, we disclose synthesis polymeric poly(FRP)s, by situ photoinduction FLP moieties, where acidic basic centers are tuned promote single electron transfer (SET). Through systematic manipulation chemical structure, demonstrate that inclusion ortho-methyl groups on phosphine monomers crucial enable SET. The generation radicals evidenced monitoring stable cations via UV/vis EPR spectroscopy. These new poly(FRP)s both catalytic hydrogenation radical-mediated photocatalytic perfluoroalkylations. systems open avenues design novel polymers for catalysis photoelectrical chemistry.

Language: Английский

Defect-Induced Synergetic Effect of Bi-Based Compounds for One-Pot Conversion of Organic Pollutants into CO via Coupling Photodegradation of Carbamazepine with Photoreduction of CO2 DOI
Lingling Zheng, Lei Tian,

Longshuai Zhang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2134 - 2143

Published: Jan. 25, 2024

The waste of carbon sources and greenhouse gas production during wastewater treatment have become extremely important environmental issues. Herein, the BiOBr/BiVO4 compounds with defect-induced frustrated Lewis acid–base pairs (DFLPs) internal charge transfer were fabricated to convert organic pollutants into CO nearly 100% selectivity. oxygen vacancy (Ov) induced built-in electric field in create directional from BiOBr BiVO4. Density functional theory (DFT) calculations prove that Ov combines its adjacent hydroxyls form DFLP active sites can additionally capture activate CO2. Meanwhile, reduce formation-free energy COOH* intermediates, which is key rate-limiting step CO2 high This system has achieved selective conversion value-added chemicals pollutant degradation provides a theoretical basis for actual recycling sources.

Language: Английский

Citations

33
A review of frustrated Lewis pair enabled monoselective C–F bond activation DOI Creative Commons
Kenneth Lye, Rowan D. Young

Chemical Science, Journal Year: 2024, Volume and Issue: 15(8), P. 2712 - 2724

Published: Jan. 1, 2024

Frustrated Lewis pair (FLP) bond activation chemistry has greatly developed over the last two decades since seminal report of metal-free reversible hydrogen activation. Recently, FLP systems have been utilized to allow monoselective C-F (at equivalent sites) in polyfluoroalkanes. The problem 'over-defluorination' functionalization polyfluoroalkanes (where multiple fluoro-positions are uncontrollably functionalized) a long-standing chemical fluorocarbon for 80 years. mediated is complementary other solutions address and offers several advantages unique opportunities. This perspective highlights some these opportunities places development into context wider effort overcome 'over-defluorination'.

Language: Английский

Citations

20
Advances in CO2 activation by frustrated Lewis pairs: from stoichiometric to catalytic reactions DOI Creative Commons
Md. Nasim Khan, Yara van Ingen,

Tribani Boruah

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(47), P. 13661 - 13695

Published: Jan. 1, 2023

Frustrated Lewis pair systems have been explored efficiently in homogeneous and heterogeneous conditions for the activation reduction of CO 2 to various useful products stoichiometric as well catalytic reactions.

Language: Английский

Citations

34
Frustrated Radical Pairs in Organic Synthesis DOI
Minsoo Ju, Zhipeng Lu, Luiz F. T. Novaes

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(36), P. 19478 - 19489

Published: Sept. 1, 2023

Frustrated radical pairs (FRPs) describe the phenomenon that two distinct radicals─which would otherwise annihilate each other to form a closed-shell covalent adduct─can coexist in solution, owing steric repulsion or weak bonding association. FRPs are typically formed via spontaneous single-electron transfer between sterically encumbered precursors─an oxidant and reductant─under ambient conditions. The components of FRP exhibit orthogonal chemical properties can often act cooperativity achieve interesting reactivities. Initially observed study traditional frustrated Lewis pairs, have recently been shown be capable homolytically activating various bonds. In this Perspective, we will discuss discovery FRPs, their fundamental reactivity bond activation, recent developments use synthetic organic chemistry, including C–H functionalization. We anticipate provide new reaction strategies for solving challenging problems modern synthesis.

Language: Английский

Citations

33
Metal‐Free Catalytic Formation of a Donor‐Acceptor‐Donor Molecule and Its Lewis Acid‐Adduct Singlet Diradical with High‐Efficient NIR‐II Photothermal Conversion DOI

Shanshan Kong,

Li‐Ming Yang,

Quanchun Sun

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: March 5, 2024

Abstract We have synthesized a quinone‐incorporated bistriarylamine donor‐acceptor‐donor (D–A–D) semiconductor 1 by B(C 6 F 5 ) 3 (BCF) catalyzed C−H/C−H cross coupling via radical ion pair intermediates. Coordination of Lewis acids BCF and Al(OR (R =C(CF to the afforded diradical zwitterions 2 integer electron transfer. Upon binding acids, LUMO energy is significantly lowered band gap narrowed from 1.93 eV ( 1.01 1.06 ). are rare near‐infrared (NIR) dyes with broad absorption both centered around 1500 nm. By introducing photo generator, can be generated light‐dependent control. Furthermore, transfer process also reversibly regulated addition CH CN. In addition, temperature sharply increased reached as high 110 °C in 10 s upon irradiation near‐infrared‐II (NIR‐II) laser (1064 nm, 0.7 W cm −2 ), exhibiting fast response laser. It displays excellent photothermal stability (PT) conversion efficiency 62.26 % high‐quality PT imaging.

Language: Английский

Citations

8
Recent Advances on C—H Functionalization via Oxidative Electrophotocatalysis DOI

Aman Hasil,

Rui Chang,

Juntao Ye

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(3), P. 728 - 728

Published: Jan. 1, 2024

Language: Английский

Citations

8
Access to Bis-Silylene-Stabilized Group 13 Cations DOI
Moushakhi Ghosh, Prakash Panwaria, Srinu Tothadi

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 6, 2025

Herein, we report the isolation of pyridine moiety-functionalized SiNSi pincer-based bis-silylene ligand (1) and its reactivity toward various halide precursors (X = Br I) group 13 elements (M Al, Ga, In). This gave us straightforward access to pincer-coordinated cations (2–7). These complexes are duly characterized by single-crystal X-ray diffraction studies, multinuclear magnetic resonance spectroscopy (1H, 13C, 29Si), high-resolution mass spectrometry techniques. Their electronic properties were further analyzed with help quantum chemical calculations.

Language: Английский

Citations

1
Heterogeneous Frustrated Lewis Pair Catalysts: Rational Structure Design and Mechanistic Elucidation Based on Intrinsic Properties of Supports DOI Creative Commons
Jiasi Li, Guangchao Li, Shik Chi Edman Tsang

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

ConspectusThe discovery of reversible hydrogenation using metal-free phosphoborate species in 2006 marked the official advent frustrated Lewis pair (FLP) chemistry. This breakthrough revolutionized homogeneous catalysis approaches and paved way for innovative catalytic strategies. The unique reactivity FLPs is attributed to base (LB) acid (LA) sites either spatial separation or equilibrium, which actively react with molecules. Since 2010, heterogeneous FLP catalysts have gained increasing attention their ability enhance performance through tailored surface designs improved recyclability, making them promising industrial applications. Over past 5 years, our group has focused on investigating strategically modifying various types solid that are from classic FLPs. We explored systematic characterization techniques unravel underlying mechanisms between active reactants. Additionally, we demonstrated critical role catalysts' intrinsic electronic geometric properties promoting formation stimulating synergistic effects. been greatly enhanced by use advanced such as synchrotron X-ray diffraction, neutron powder photoelectron spectroscopy, extended absorption fine structure, elemental mapping scanning transmission electron microscopy, paramagnetic resonance diffuse-reflectance infrared Fourier transform solid-state nuclear magnetic spectroscopy. These provided deeper insights into structural systems future design catalysts.Understanding distribution overlapping orbitals LA LB pairs essential inducing operando target reallocation external stimuli. For instance, silicoaluminophosphate-type zeolites weak orbital overlap, adsorption polar gas molecules leads heterolytic cleavage Alδ+–Oδ− bond, creating unquenched LA–LB pairs. In a Ru-doped metal–organic framework, Ru–N bond can be polarized metal–ligand charge transfer under light, forming Ru+–N– activation framework represents groundbreaking innovation expands potential existing materials. already employing chemistry dynamically generate products substrates, complete mechanistic interpretation requires thorough examination surrounding environment. hydrogen spillover surfaces improves conversion efficiency suppressing poisoning at metal sites. situ H2–H2O conditions enable production organic chemicals excellent activity selectivity new bifunctional via By highlighting novel featuring induction effects selection elucidate reaction mechanisms, hope this Account will offer strategies designing characterizing research community.

Language: Английский

Citations

1
Iodoarene Activation: Take a Leap Forward toward Green and Sustainable Transformations DOI Creative Commons
Toshifumi Dohi, Elghareeb E. Elboray, Kotaro Kikushima

et al.

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Constructing chemical bonds under green sustainable conditions has drawn attention from environmental and economic perspectives. The dissociation of (hetero)aryl-halide is a crucial step most arylations affording (hetero)arene derivatives. Herein, we summarize the (hetero)aryl halides activation enabling direct (hetero)arylation trapping reagents construction highly functionalized (hetero)arenes benign conditions. strategies for aryl iodides are classified into (a) hypervalent iodoarene followed by functionalization thermal/photochemical conditions, (b) aryl-I bond in presence bases with/without organic catalysts promoters, (c) photoinduced presence/absence organophotocatalysts, (d) electrochemical direct/indirect electrolysis mediated organocatalysts mediators acting as electron shuttles, (e) electrophotochemical redox-active organocatalysts. These modes result exhibiting diverse reactivity formal cations/radicals/anions aryne precursors. coupling these reactive intermediates with leads to facile selective formation C-C C-heteroatom bonds. ecofriendly, inexpensive, functional group-tolerant offer alternatives transition metal-based catalysis.

Language: Английский

Citations

1
Synthesis of zwitterionic open-shell bilayer spironanographenes DOI Creative Commons
Juan Lión‐Villar, Jesús M. Fernández‐García, Samara Medina Rivero

et al.

Nature Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 30, 2025

Language: Английский

Citations

1