Unique Properties and Emerging Applications of Carbolong Metallaaromatics

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(8), P. 924 - 937

Published: Jan. 31, 2023

ConspectusAromatic compounds are important in synthetic chemistry, biomedicines, and materials science. As a special type of aromatic complex, transition-metal-based metallaaromatics contain at least one transition metal an framework. The chemistry has seen much progress computational studies methods, but their properties applications still emerging. In recent years, we have disclosed series metal-centered conjugated polycyclic metallacycles which carbon chain is chelated to center through three metal-carbon bonds. These termed carbolong complexes exhibit good stability water, oxygen, light, heat on account polydentate chelation aromaticity, making them easy handle. Carbolong not only π-conjugated aromatics also organometallics; therefore, they the both species. this Account, showcase advances based different properties.First, kind aromatic, with ability transmit electrons, allowing function as single-molecule conductors candidates for electron transporting layer (ETLs) solar cells. A been proved be useful achievable ETLs enhance device performance organic cells perovskite cells.Second, due involvement d orbitals conjugation, normally strong broad absorption, even some cases extending near-infrared region (NIR). absorbed optical energy can converted into heat, ultrasound; consequently, used core moieties smart materials. For example, 7C were found aggregation-enhanced emission (AIEE). Some 12C designed NIR-responsive polymers, such cylindrical materials, self-healing shape memory contrast stereotypically toxic osmium highly OsO4, low cell cytotoxicity biocompatibility; potential biomedical area. benefiting from absorption NIR, 9C photoacoustic imaging photothermal therapy, respectively. addition, photodynamic therapeutic take advantage peroxo complex discussed.Third, transition-metal by carbon-based ligands, displayed catalytic activity dehydrogenation alcohols bimetallic catalyze difunctionalization reactions unactivated alkenes.Overall, applied photovoltaics, phototherapy, reactions. Moving forward, hope that Account will shed light future theoretical research encourage more discoveries other metallaaromatics.

Language: Английский

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Syntheses and reactivities of strained fused-ring metallaaromatics containing planar eleven-carbon chains

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 23, 2024

Abstract Carbolong complexes are one of the primary types metallaaromatics, and they include metallapentalynes metallapentalenes. A series 7C-10C 12C-carbolong with planar ligand skeletons respectively containing 7-10 12 carbon atoms in their backbones, have been previously reported. Herein, two classes strained substances, metallabenzyne-fused metallapentalenes metallabenzene-fused metallapentalynes, were prepared, both representing 11C-carbolong a carbon-chain ligand. Furthermore, former type is also carbolong derivatives metallabenzyne skeleton, another metallaaromatic framework. Metallabenzyne-fused show versatile reactivities, most interesting metal carbyne bond shift from 6-membered to more 5-membered ring, affording above-mentioned metallapentalyne. This work makes chemistry complete, provides method achieve metallabenzynes, which anticipated concurrently advance development these metallaaromatics.

Language: Английский

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Developing multi-functional anthraquinone-based conjugated porous polymers for near-infrared-light-driven high selective cyanation of α-amino C(sp3)-H bonds

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 8, 2025

Language: Английский

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Fusion of Four Aromatic Rings via an Atom-Mutual-Embedding Strategy to Form a Tetrahexacyclic System

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

Skeletal manipulation of aromatic compounds has emerged as a potent tool in synthetic chemistry, but simultaneous multiring remains largely unexplored due to the inherent complexities ring and site selectivity. Herein, we report an unprecedented skeletal that fuses four 5-membered rings, comprising two organic metal-containing systems, into novel metal-bridged 6/6/6/6-membered scaffold. The sequential fusion is accomplished through atom-mutual-embedding strategy; this strategy entails stepwise insertion nitrogen atoms separate metal-carbon bonds simultaneously integrates metal atom bridge across isoxazole moieties. presence central crucial for ensuring precise substrate alignment enhancing both specificity. resulting tetrahexacyclic products exhibit remarkable stability superior near-infrared (NIR) functional properties, surpassing those precursor compounds. This work not only establishes conceptual foundation designing versatile molecules amenable intricate editing also contributes rational performance-targeted molecular architectures.

Language: Английский

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Osmathiazole Ring: Extrapolation of an Aromatic Purely Organic System to Organometallic Chemistry

Organometallics, Journal Year: 2023, Volume and Issue: 42(4), P. 327 - 338

Published: Feb. 9, 2023

An osmathiazole skeleton has been generated starting from the cation of salt [OsH(OH)(≡CPh)(IPr)(PiPr3)]OTf (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene; OTf CF3SO3) and thioacetamide; its aromaticity degree was compared with that thiazole, aromatic reactivity confirmed through a reaction phenylacetylene. Salt 1 reacts thioamide to initially afford synthetic intermediate [OsH{κ2-N,S-[NHC(CH3)S]}(≡CPh)(IPr)(PiPr3)]OTf (2). Thioamidate alkylidyne ligands 2 couple in acetonitrile at 70 °C, forming 1:1 mixture salts [OsH{κ2-C,S-[C(Ph)NHC(CH3)S]}(CH3CN)(IPr)(PiPr3)]OTf (3) [Os{κ2-C,S-[CH(Ph)NHC(CH3)S]}(CH3CN)3(IPr)]OTf (4). Treatment 3 potassium tert-butoxide produces NH-deprotonation five-membered ring gives OsH{κ2-C,S-[C(Ph)NC(CH3)S]}(IPr)(PiPr3) (5). The 5 is slightly less than osmathiazolium cycle purely organic thiazole. However, it more related osmaoxazoles osmaoxazoliums. There are significant differences behavior between toward In acetonitrile, loses phosphine adds alkyne [Os{η3-C3,κ1-S-[CH2C(Ph)C(Ph)NHC(CH3)S]}(CH3CN)2(IPr)]OTf (6), bearing functionalized allyl ligand. contrast, undergoes vicarious nucleophilic substitution hydride, by acetylide, via dihydride OsH2(C≡CPh){κ2-C,S-[C(Ph)NC(CH3)S]}(IPr)(PiPr3) (7), which releases H2 yield Os(C≡CPh){κ2-C,S-[C(Ph)NC(CH3)S]}(IPr)(PiPr3) (8).

Language: Английский

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Ag-Catalyzed Practical Synthesis of N-Acyl Anthranilic Acids from Anthranils and Carboxylic Acids

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(5), P. 3150 - 3160

Published: Feb. 9, 2024

A practical synthesis of valuable N-acyl anthranilic acids has been achieved via a silver-catalyzed imino-ketene generation from readily available anthranils and carboxylic acids. wide range including sterically demanding aliphatic acids, aromatic acrylic amino are compatible in this reaction. Moreover, method can be used to modify drug molecules natural products, such as ibuprofen, probenecid, acetylglycine.

Language: Английский

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Hetero-carbolong chemistry: experimental and theoretical studies of diaza-metallapentalenes

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(28), P. 4173 - 4176

Published: Jan. 1, 2023

Treatment of azo compounds with an η 2 -alkyne-coordinated metallacycle via alkyne-azo coupling followed by aromatization efficiently afforded the first diaza-metallapentalenes.

Language: Английский

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Construction of a Metallacyclopentadiene Ring through the Attack of Carbanions to M≡C Bond Followed by C—H Activation^†

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 42(3), P. 235 - 242

Published: Sept. 4, 2023

Comprehensive Summary Metallacyclopentadienes are important metallacycles and regarded as intermediates in many reactions, therefore, new methods to achieve them anticipated. In this study, a formal [3+2] method, through the reactions of an osmapentalyne with benzyl carbanions, was developed. The underwent nucleophilic attack carbanions Os≡C bond, followed by C—H activation form five‐membered osmacyclopentadiene ring. Most were carried out at room temperature, substituents on aromatic rings diverse, resulting products contain Os—H representing novel type 10C‐carbolong complexes. This work provides convenient route construct metallacyclopentadienes, which is expected further promote development such substances.

Language: Английский

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Synthesis and Structure of Chlororuthenacyclopentatriene

Inorganic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(23), P. 8479 - 8488

Published: Jan. 1, 2024

Chlororuthenacyclopentatriene, representing a new member of the ruthenaaromatic family, was successfully prepared using reactions RuCl 2 (PPh 3 ) with o -phenyldiyne derivatives in presence excess HCl.

Language: Английский

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Host-guest assemblies for improved photothermal cancer therapy

Chemical Synthesis, Journal Year: 2023, Volume and Issue: 3(2), P. 16 - 16

Published: Jan. 1, 2023

Photothermal cancer therapy has attracted plenty of attention in the last decades due to its promising efficacy, spatiotemporal control, negligible drug resistance, etc. However, achieve widespread clinical application, enhancement curative effect and minimization side still need be concerned about field photothermal therapy. Host-guest assemblies, constructed by inclusion small molecular guests into macrocyclic hosts through non-covalent interactions, are featured with unique microenvironment flexible, dynamic nature. On basis abovementioned advantages, host-guest assemblies show great potential best our knowledge, endeavors assemblies-based have not been systematically discussed. Hence, benefit design advanced assembly-based agents promote development therapy, this review, major achievements including conversion efficiency, improvement targeted distribution tumor site, superiority constructing therapy-derived multimodal synergistic In addition, future perspectives on outlined.

Language: Английский

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