Bucket Effect to Improve <scp>Third‐Order</scp> Nonlinear Optical Response on <scp>Metal‐Heteroaromatic</scp> Compounds

Wang, Zirui; Fang, Yu‐Hui; Lin, Huaxing; Zhao, Guolin; Yan, Weiyin; Ma, Zuju; Li, Qiaohong; Zhang, Jian

doi:10.1002/cjoc.202200359

Cited by 7 publications

(5 citation statements)

References 64 publications

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“…Some properties and applications are not demonstrated in detail here, but they also show quite promising results, including the theoretical predication for applications of osmapentalynes in third-order nonlinear optical materials, − photothermal properties of metal-bridged osmaindenes, reversible oxidation of metallapentalenoxazetes, mitochondrial dysfunction by phosphonium-containing metallafurans, NIR-responsive hydrogels containing 12C carbolongs, light-mediated CO 2 -responsive metallaaromatic microgels, and hypersaline water treatment . Moreover, we have most recently prepared polycarbolong conjugated polymers that employed metallaaromatics as building blocks, exhibiting optimistic applications in conductive polymers …”

Section: Other Studies Of Properties and Applications Of Metallaaroma...mentioning

confidence: 90%

Unique Properties and Emerging Applications of Carbolong Metallaaromatics

Luo

Chen

et al. 2023

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Aromatic 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 in an aromatic framework. The chemistry of metallaaromatics has seen much progress in computational studies and synthetic methods, but their properties and applications are still emerging. In recent years, we have disclosed a series of metal-centered conjugated polycyclic metallacycles in which a carbon chain is chelated to a metal center through at least three metal−carbon bonds. These are termed carbolong complexes and exhibit good stability to water, oxygen, light, and heat on account of their polydentate chelation and aromaticity, making them easy to handle. Carbolong complexes are not only special π-conjugated aromatics but also organometallics; therefore, they have the properties of both species. In this Account, we showcase the recent advances in their applications based on their different properties.First, carbolong complexes are a special kind of π-conjugated aromatic, with the ability to transmit electrons, allowing them to function as single-molecule conductors and candidates for electron transporting layer materials (ETLs) in solar cells. A series of carbolong complexes have been proved to be useful as achievable ETLs which enhance device performance in both organic solar cells and perovskite solar cells. Second, due to the involvement of d orbitals in the conjugation, carbolong complexes normally exhibit strong and broad absorption, even in some cases extending to the near-infrared region (NIR). The absorbed optical energy can be converted into light, heat, and ultrasound; consequently, carbolong compounds can be used as core moieties in smart materials. For example, 7C carbolong complexes were found to exhibit aggregation-enhanced near-infrared emission (AIEE). Some 12C carbolong complexes have been designed into the core moieties of NIR-responsive polymers, such as cylindrical NIR-responsive materials, self-healing materials, and shape memory materials. In contrast to the stereotypically toxic osmium compounds such as the highly toxic OsO 4 , some osmium carbolong complexes exhibit low cell cytotoxicity and good biocompatibility; consequently, they also have potential applications in the biomedical area. For example, benefiting from broad absorption in the NIR, 9C and 12C carbolong complexes have been used in photoacoustic imaging and photothermal therapy, respectively. In addition, photodynamic therapeutic applications which take advantage of a carbolong peroxo complex are discussed. Third, as special transition-metal complexes chelated by carbon-based ligands, a carbolong peroxo complex has displayed catalytic activity in the dehydrogenation of alcohols and a bimetallic carbolong complex has been used to catalyze difunctionalization reactions of unactivated alkenes. Overall, aromatic carbolong complexes have been applied to photovoltaics, s...

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Section: Other Studies Of Properties and Applications Of Metallaaroma...mentioning

confidence: 90%

Unique Properties and Emerging Applications of Carbolong Metallaaromatics

Luo

Chen

et al. 2023

Acc. Chem. Res.

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“…[ 32‐33 ] The fused π‐conjugated backbones of ladder molecules exhibit high planarity and long effective conjugation length, which facilitate the intensification of absorption bands and reduce the molecular motion. [ 34‐36 ] Therefore, fused‐ring molecules typically exhibit high molar extinction coefficients ( ɛ ) and high emission quantum yields. [ 37‐39 ] Notably, the triplet energy level can be reduced by the extension of conjugation.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Organic Host‐Guest Materials with Bright Red Room‐Temperature Phosphorescence for Persistent Bioimaging^†

Zhao

Dai

et al. 2023

Chin. J. Chem.

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Comprehensive Summary Organic room‐temperature phosphorescence (RTP) materials have attracted immense attention in bioimaging due to their long emission lifetime and large Stokes shift. RTP materials with long emission wavelength can improve the penetration depth for bioimaging. However, the design of red persistent RTP materials is still challenging. In this study, a fused‐ring structure has been proposed to effectively decrease the triplet energy level, thus extending the emission wavelength of phosphorescence. In addition, the fused‐ring structure exhibits a high molar extinction coefficient (ɛ) and high luminescence efficiency due to the rigid structure. A new class of crystalline hosts (iminodibenzyl, IDB) are developed to stabilize the triplet excitons that are generated from the fused‐ring molecules. The maximum RTP wavelength of doping materials can reach 635 nm with a lifetime of 9.35 ms. Water‐disperse nanoparticles are successfully prepared for in vivo time‐resolved bioimaging, which eliminates the background fluorescence interference from biological tissues. These reveal a delicate design strategy for the construction of long‐wavelength emissive RTP materials for high‐resolution bioimaging.

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“…Conjugated metallacycles have gained increasing interests due to their unique structures, [ 12‐13 ] diverse reactivity, [ 14 ] unusual aromaticity, [ 15 ] distinctive properties, and promising applications. [ 16 ] Thanks to transition metals capable of owning several metal‐carbon bonds, the metal‐bridgehead conjugated polycyclic systems such as spiro metalloles, [ 17 ] metallapentalene derivatives, [ 18 ] and metal‐bridged metallabenzene derivatives [ 19 ] have been realized. Though various bicyclic and tricyclic conjugated metallacycles have been isolated, [ 12,20 ] the tetracyclic conjugated frameworks in which the metal is incorporated into four conjugated rings and that generally exhibit excellent photophysical properties are rarely explored.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Formal [2+1] Cycloadditions of a Metallacyclopentadiene Unit with Alkynes: Constructing Tetracyclic Conjugated Frameworks with Bridgehead Metals

Chu

Chen

et al. 2023

Chin. J. Chem.

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Comprehensive Summary Metallacyclopentadienes play a vital role in transition‐metal mediated and catalyzed cycloaddition reactions of alkynes. Though versatile reactions of metallacyclopentadienes with alkynes have been disclosed, [2+1] cycloadditions of metallacyclopentadienes and alkynes have never been discovered. In present work, we report the formal [2+1] cycloadditions of a metallacyclopentadiene unit with a broad scope of commercial alkynes, providing a facile strategy to construct tetracyclic conjugated compounds. The deuterated experiment indicates a metal vinylidene intermediate has been involved in [2+1] cycloaddition. Moreover, the electrophilic substitution reaction of the tetracyclic conjugated compound with the aid of density functional theory (DFT) calculated Fukui functions is investigated. These tetracyclic conjugated compounds exhibit broad absorption spectra in the whole visible region which could be employed as potential photovoltaic materials.

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Bucket Effect to Improve Third‐Order Nonlinear Optical Response on Metal‐Heteroaromatic Compounds

Cited by 7 publications

References 64 publications

Unique Properties and Emerging Applications of Carbolong Metallaaromatics

Unique Properties and Emerging Applications of Carbolong Metallaaromatics

Organic Host‐Guest Materials with Bright Red Room‐Temperature Phosphorescence for Persistent Bioimaging^†

Formal [2+1] Cycloadditions of a Metallacyclopentadiene Unit with Alkynes: Constructing Tetracyclic Conjugated Frameworks with Bridgehead Metals

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Bucket Effect to Improve Third‐Order Nonlinear Optical Response on Metal‐Heteroaromatic Compounds

Cited by 7 publications

References 64 publications

Unique Properties and Emerging Applications of Carbolong Metallaaromatics

Unique Properties and Emerging Applications of Carbolong Metallaaromatics

Organic Host‐Guest Materials with Bright Red Room‐Temperature Phosphorescence for Persistent Bioimaging†

Formal [2+1] Cycloadditions of a Metallacyclopentadiene Unit with Alkynes: Constructing Tetracyclic Conjugated Frameworks with Bridgehead Metals

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Product

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Organic Host‐Guest Materials with Bright Red Room‐Temperature Phosphorescence for Persistent Bioimaging^†