A conjugated diosma-octacyclic complex and its mixed-valence singly reduced state

Hu, Yuxuan; Deng, Qianqian; Ou, Ya‐Ping; Yang, Xiaofei; Zhang, Jing; Garrett, Emily K.; Zhu, Jun; Liu, Shenghua; Hartl, František

doi:10.1039/d2qi01523d

Cited by 4 publications

(2 citation statements)

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“…In 2022, Liu and co‐workers synthesized conjugated dicationic dinuclear compounds 52 and 53 (Figure 16A) with the aromatic osmapentalene termini connected to the rigid naphthalate bridge by the non‐aromatic osmafuran moiety [110] . The downfield proton chemical shifts, induced current density (AICD) analyses, and calculated electron density of delocalized bonds (EDDB) values confirmed the aromaticity of the terminal osmapentalene unit and bridge core.…”

Section: Electronic Properties Of Metallaaromaticsmentioning

confidence: 92%

Metallaaromatic Complexes as Candidates for Future Molecular Materials and Electronic Devices: Recent Advancements

Yang,

Zhang,

Liu

et al. 2023

Chemistry An Asian Journal

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In recent years, the field of organometallic chemistry has made a great progress and diverse types of metallaaromatics have successively been reported. In those studies, incorporation of ligated osmium centers into metallaaromatic systems played a prominent role. The reviewed literature documents that certain metallaaromatics with unconventional photophysical properties, redox and electronic transport properties and magnetism, have potential to be widely used in diverse practical applications, with selected examples of amino acid and fluoride anion identification, photothermal effects, functional materials, photodynamic therapy (PDT) in biomedicine, single‐molecule junction conductors, and electron‐transport layer materials (ETLs) in solar cells.

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Section: Electronic Properties Of Metallaaromaticsmentioning

confidence: 92%

Metallaaromatic Complexes as Candidates for Future Molecular Materials and Electronic Devices: Recent Advancements

Yang,

Zhang,

Liu

et al. 2023

Chemistry An Asian Journal

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“…[ 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. [ 14b,21 ] Herein, we report the novel reaction mode of a metallacyclopentadiene unit with terminal alkynes where formal [2+1] cycloadditions proceed, leading to planar tetracyclic conjugated frameworks with bridgehead metals (Scheme 1b).…”

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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Synthesis and Characterization of a Rhenanaphthalene Isomer

Wang

Zheng

et al. 2023

Chemistry A European J

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Exploration of organometallic metallacycles has led to the development of various polycyclic compounds with fascinating structures, which could be used as functional materials. In this work, a new rhenanaphthalene isomer was isolated from the reaction of ReH5(PMe2Ph)3 with o‐ethynylphenyl alkyne in the presence of excess HCl. Its structure was then identified using the single‐crystal X‐ray diffraction and NMR spectroscopy. DFT studies suggest that its formation involves two protonation reactions and two migration reactions. This new rhenanaphthalene isomer enriches the family of metallacycles.

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A conjugated diosma-octacyclic complex and its mixed-valence singly reduced state

Abstract: Metallaaromatics as a new class of organometallic compounds have attracted considerable attention in recent years. Metallaaromatic compounds where the number of fused rings forming the metalla-polycyclic skeleton exceeds seven have...

Cited by 4 publications

References 74 publications

Metallaaromatic Complexes as Candidates for Future Molecular Materials and Electronic Devices: Recent Advancements

Metallaaromatic Complexes as Candidates for Future Molecular Materials and Electronic Devices: Recent Advancements

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

Synthesis and Characterization of a Rhenanaphthalene Isomer

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