Naphtho- and anthra-disilacyclobutadienes

Ishida, Shintaro; Sugawara, Shohei; Honda, Shunya; Iwamoto, Takeaki

doi:10.1039/d0cc06603f

Cited by 7 publications

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References 49 publications

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“…The novel spiropentasiladiene 2 was obtained in the form of orange-red crystals from the reduction of dibromochlorosilane 3 with KC 8 in THF at −30 °C (Scheme ). 3 bears the bulky alkyl group 1,1-bis(trimethylsilyl)-3,3-dimethylbutyl, which is hereafter abbreviated to Rs . The characterization of 2 was achieved using NMR and UV–vis spectroscopy, mass spectrometry (MS), as well as single-crystal X-ray diffraction (XRD) analysis.…”

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confidence: 75%

A Spiropentasiladiene Radical Cation: Spin and Positive Charge Delocalization across Two Perpendicular Si═Si Bonds and UV–vis–NIR Absorption in the IR-B Region

et al. 2021

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Spiroconjugation, that is, through-space orbital interactions between two perpendicular π orbitals, is a key concept in the contemporary molecular design of spirocyclic π-electron systems. We synthesized spiropentasiladiene radical cation salt 1 as a dark-green solid via the one-electron oxidation of the stable spiropentasiladiene 2. Characterization of the molecular structure combined with theoretical studies indicated that the spin and positive charge are delocalized across the two perpendicular SiSi double bonds of 1. Two π(SiSi) orbitals are split into HOMO and SOMO with a small energy gap owing to the second-order Jahn–Teller distortion and steric repulsion between bulky alkyl groups upon one-electron oxidation. In the UV–vis–NIR spectrum, the longest-wavelength absorption band of 1 (λmax = 1972 nm) covers the IR-B region (1400–3000 nm; 0.89–0.41 eV) despite having the smallest possible spiroconjugation motif. The unprecedented absorption band in the IR region was assigned to the HOMO → SOMO transition that arises from the delocalized π-orbitals in the spirocyclic Si5 skeleton.

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confidence: 75%

A Spiropentasiladiene Radical Cation: Spin and Positive Charge Delocalization across Two Perpendicular Si═Si Bonds and UV–vis–NIR Absorption in the IR-B Region

et al. 2021

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Computational and Theoretical Aspects of Structure and Bonding in Doubly Bonded Organogermanium Compounds

Karni¹,

Apeloig²

2023

Organogermanium Compounds

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Experimental and Theoretical Characterization of 4π‐Electron Möbius Aromatic System of a 1,2‐Digermacyclobutadiene^†

Sugahara,

Hashizume,

Espinosa Ferao

et al. 2024

Angewandte Chemie

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We present the visualization of the experimental valence electron‐density distribution (EDD) in the isolated 1,2‐digermacyclobutadiene ring system, revealing the unique 4π electron‐delocalization on the four‐membered Ge2C2 ring. A remarkably high Möbius 4π‐electron aromatic character in the Ge2C2 ring can be suggested from theoretical calculations, in sharp contrast to the significant antiaromaticity of the all‐carbon cyclobutadiene ring.

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Naphtho- and anthra-disilacyclobutadienes

Abstract: Naphthodislacyclobutadiene 3 and anthradisilacyclobutadiene 4 were synthesized and characterized. In these compounds, diatropic ring current on the benzene ring adjacent to the disilacyclobutadiene moiety decreases while that on the other...

Cited by 7 publications

References 49 publications

A Spiropentasiladiene Radical Cation: Spin and Positive Charge Delocalization across Two Perpendicular Si═Si Bonds and UV–vis–NIR Absorption in the IR-B Region

A Spiropentasiladiene Radical Cation: Spin and Positive Charge Delocalization across Two Perpendicular Si═Si Bonds and UV–vis–NIR Absorption in the IR-B Region

Computational and Theoretical Aspects of Structure and Bonding in Doubly Bonded Organogermanium Compounds

Experimental and Theoretical Characterization of 4π‐Electron Möbius Aromatic System of a 1,2‐Digermacyclobutadiene^†

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Naphtho- and anthra-disilacyclobutadienes

Abstract: Naphthodislacyclobutadiene 3 and anthradisilacyclobutadiene 4 were synthesized and characterized. In these compounds, diatropic ring current on the benzene ring adjacent to the disilacyclobutadiene moiety decreases while that on the other...

Cited by 7 publications

References 49 publications

A Spiropentasiladiene Radical Cation: Spin and Positive Charge Delocalization across Two Perpendicular Si═Si Bonds and UV–vis–NIR Absorption in the IR-B Region

A Spiropentasiladiene Radical Cation: Spin and Positive Charge Delocalization across Two Perpendicular Si═Si Bonds and UV–vis–NIR Absorption in the IR-B Region

Computational and Theoretical Aspects of Structure and Bonding in Doubly Bonded Organogermanium Compounds

Experimental and Theoretical Characterization of 4π‐Electron Möbius Aromatic System of a 1,2‐Digermacyclobutadiene†

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Experimental and Theoretical Characterization of 4π‐Electron Möbius Aromatic System of a 1,2‐Digermacyclobutadiene^†