Facile Construction of New Hybrid Conjugation via Boron Cage Extension

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(6), С. 3577 - 3587

Опубликована: Фев. 6, 2023

Aromatic polycyclic systems have been extensively utilized as structural subunits for the preparation of various functional molecules. Currently, aromatics-based are predominantly generated from extension two-dimensional (2D) aromatic rings. In contrast, compounds based on three-dimensional (3D) aromatics such boron clusters less studied. Here, we report three types cluster-cored tricyclic molecular systems, which constructed a 2D ring, 3D nido-carborane, and an alkyne. These new can be facilely accessed by Pd-catalyzed B-H activation subsequent cascade heteroannulation carborane pyridine with alkyne in isolated yield up to 85% under mild conditions without any additives. Computational results indicate that newly ring fusion carborane, pyridyl is non-aromatic. However, not only leads 1H chemical shift considerably downfield shifted owing strong diatropic current embedded but also devotes new/improved physicochemical properties including increased thermal stability, emergence absorption band, largely red-shifted emission band enhanced efficiency. Besides, number bright, color-tunable solid emitters spanning over all visible light obtained absolute luminescence efficiency 61%, contrast aggregation-caused quenching of, e.g., Rhodamine B containing 2D-aromatics-fused structure. This work demonstrates hybrid conjugated might promising scaffolds construction

Язык: Английский

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Photoinduced Selective B–H Activation of nido-Carboranes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(11), С. 7791 - 7802

Опубликована: Март 10, 2024

The development of new synthetic methods for B–H bond activation has been an important research area in boron cluster chemistry, which may provide opportunities to broaden the application scope clusters. Herein, we present a reaction strategy direct site-selective functionalization nido-carboranes initiated by photoinduced cage via noncovalent cage···π interaction. As result, nido-carborane radical is generated through single electron transfer from 3D 2D photocatalyst upon irradiation with green light. resulting transient could be directly probed advanced time-resolved EPR technique. In air, subsequent transformations active have led efficient and selective B–N, B–S, B–Se couplings presence N-heterocycles, imines, thioethers, thioamides, selenium ethers. This protocol also facilitates both late-stage modification drugs synthesis nido-carborane-based drug candidates neutron capture therapy (BNCT).

Язык: Английский

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Electrochemical Cage Activation of Carboranes

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(20)

Опубликована: Фев. 11, 2022

Abstract Carboranes are boron–carbon molecular clusters that possess unique properties, such as their icosahedron geometry, high boron content, and delocalized three‐dimensional aromaticity. These features render carboranes valuable building blocks for applications in supramolecular design, nanomaterials, optoelectronics, organometallic coordination chemistry, neutron capture therapy (BNCT) agents. Despite tremendous progress this field, stoichiometric chemical redox reagents largely required the oxidative activation of carborane cages. In context, electrosyntheses represent an alternative strategy more sustainable syntheses. It is only recent few years considerable has been made electrochemical cage functionalization carboranes, which summarized Minireview. We anticipate electrocatalysis will serve increasingly powerful stimulus within current renaissance electrochemistry.

Язык: Английский

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Carborane-based BODIPY dyes: synthesis, structural analysis, photophysics and applications

Frontiers in Chemistry, Год журнала: 2024, Номер 12

Опубликована: Ноя. 5, 2024

Icosahedral boron clusters-based BODIPY dyes represent a cutting-edge class of compounds that merge the unique properties clusters with exceptional fluorescence characteristics dyes. These kinds molecules have garnered substantial interest due to their potential applications across various fields, mainly including optoelectronics, bioimaging, and use as carriers for Boron Neutron Capture Therapy (BNCT). Carborane are known stability, rigid geometry, 3D-aromaticity, while renowned strong absorption, high quantum yields, photostability. The integration carborane into structures leverages stability versatility carboranes enhancing photophysical BODIPY-based fluorophores. This review explores synthesis structural diversity dyes, highlighting how incorporation can lead significant changes in electronic optical We discuss enhanced characteristics, such red-shifted absorption emission poperties, charge transfer effects, improved cellular uptake, resulting from substitution. also delves diverse these compounds. In carborane-BODIPY offer superior internalization, making them ideal cell tracking. photodynamic therapy, (PDT) act potent photosensitizers capable generating reactive oxygen species (ROS) targeted cancer treatment excellent candidates PDT. Additionally, make suitable optoelectronic applications, organic light-emitting diodes (OLEDs) sensors. Overall, versatile promising materials innovation scientific technological applications. aims provide comprehensive overview current state research on synthesis, properties, broad application spectrum.

Язык: Английский

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Charge-Compensated Derivatives of Nido-Carborane

Inorganics, Год журнала: 2023, Номер 11(2), С. 72 - 72

Опубликована: Фев. 2, 2023

This review summarizes data on the main types of charge-compensated nido-carborane derivatives. Compared with organic analogs, onium derivatives have increased stability due to stabilizing electron-donor action boron cage. Charge-compensated are considered according type heteroatom bonded a atom.

Язык: Английский

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Electrooxidative B−H Functionalization of nido‐Carboranes

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(14), С. 7838 - 7844

Опубликована: Дек. 29, 2020

Abstract An atom‐economical method for the direct B−H functionalization of nido ‐carboranes (7,8‐ ‐C 2 B 9 H 12 − ) has been developed under electrochemical reaction conditions. In this system, anodic oxidation serves as a green alternative traditional chemical oxidants in ‐carboranes. No transition‐metal catalyst is required and different heteroatoms bearing lone pair are reactive transformation. Coupling with thioethers, selenides, tellurides, N‐heterocycles, phosphates, phosphines, arsenides antimonides demonstrates high site‐selectivity efficiency. Importantly, can be easily incorporated into drug motifs through protocol.

Язык: Английский

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Palladium‐Catalyzed Hydroboration of Alkynes with Carboranes: Facile Construction of a Library of Boron Cluster‐Based AIE‐Active Luminogens

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(33)

Опубликована: Июнь 6, 2022

Abstract The classical aggregation‐induced emission (AIE)‐active luminogens (AIEgens) usually include two‐dimensional aromatic systems such as tetraphenylethenes, which are synthesized in several steps by using toxic additives. Here, we proposed a new molecular design strategy for the realization of AIE properties combining three‐dimensional boron clusters carboranes with vinyl group(s). To obtain library cluster‐based AIEgens, Pd‐catalyzed hydroboration alkynes is reported. This reaction protocol proceeds one step under mild conditions rapid rate, excellent yields and regioselectivity. Photophysical property studies demonstrate that facile motions solution can be inhibited solid state these molecules, leads to interesting properties. work provides not only general principle AIEgens but also an efficient methodology synthesize photo‐functional molecules.

Язык: Английский

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Electrochemical B−H Nitrogenation: Access to Amino Acid and BODIPY‐Labeled nido‐Carboranes

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(3), С. 1482 - 1487

Опубликована: Сен. 29, 2020

Electrocatalyzed oxidative B-H nitrogenations of nido-carborane (nido-7,8-C

Язык: Английский

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Rhodium-Catalyzed B(4)–H and B(3)–H Alkylation Reaction of Pyridyl o-Carboranes with α-Diazodicarboxylates

Organic Letters, Год журнала: 2022, Номер 24(7), С. 1507 - 1512

Опубликована: Фев. 10, 2022

An efficient Rh-catalyzed B(4)-H and B(3)-H alkylation reaction was demonstrated from the reactions of a variety pyridyl o-carboranes with α-diazodicarboxylates release molecular nitrogen, leading to production alkylated in good excellent yields high selectivity, wide substrate scope, functional group tolerance.

Язык: Английский

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Formation and reactivity of a unique M⋯C–H interaction stabilized by carborane cages

Chemical Science, Год журнала: 2024, Номер 15(24), С. 9274 - 9280

Опубликована: Янв. 1, 2024

Broadening carborane applications has consistently been the goal of chemists in this field. Herein, compared to alkyl or aryl groups, a cage demonstrates an advantage stabilizing unique bonding interaction: M⋯C–H interaction.

Язык: Английский

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