9,9'-Bi(xanthene)-Type Hexaphenylethane Derivatives as Advanced Organic Electrochromic Systems

Silaspiranes have attracted particular attention due to their chiral spiro‐silicon center, which serves as an ideal carbon isostere and can endow spiro‐analogs with distinct properties. Distinct from previously reported cyclization or cycloaddition strategies to form 5/5‐silaspiranes, we report herein the asymmetric dual ring expansion of spirosilabicyclobutanes with alkynes to synthesize axially chiral spirosilabicyclohexenes bearing a novel 6/6‐silaspirane framework. DFT (density functional theory) calculations provide the deep insight into the origin of the high enantioselectivity controlled by the sterically demanding binaphthyl phosphoramidite ligand. Preliminary studies of chiroptical properties indicate that one of the spirosilabicyclohexene analogs exhibit fluorescence emission, Cotton effects and CPL (circularly polarized luminescence) activity.

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Enantioselective Synthesis of Spirosilabicyclohexenes by Asymmetric Dual Ring Expansion of Spirosilabicyclobutane with Alkynes

Chen

Peng

Pang

et al. 2022

Angewandte Chemie

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Enantioselective Synthesis of Spirosilabicyclohexenes by Asymmetric Dual Ring Expansion of Spirosilabicyclobutane with Alkynes

et al. 2022

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Silaspiranes have attracted particular attention due to their chiral spiro-silicon center, which serves as an ideal carbon isostere and can endow spiro-analogs with distinct properties. Distinct from previously reported cyclization or cycloaddition strategies to form 5/5-silaspiranes, we report herein the asymmetric dual ring expansion of spirosilabicyclobutanes with alkynes to synthesize axially chiral spirosilabicyclohexenes bearing a novel 6/6-silaspirane framework. DFT (density functional theory) calculations provide the deep insight into the origin of the high enantioselectivity controlled by the sterically demanding binaphthyl phosphoramidite ligand. Preliminary studies of chiroptical properties indicate that one of the spirosilabicyclohexene analogs exhibit fluorescence emission, Cotton effects and CPL (circularly polarized luminescence) activity.

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Near‐Infrared Electrochromic Behavior of Dibenzothiepin Derivatives Attached with Two Michler's Hydrol Blue Units

Ishigaki

Takata

Shimajiri

et al. 2022

Chemistry A European J

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10,11-Bis[bis(4-dimethylaminophenyl)methylene]dibenzo [bf]thiepin (1) and -oxepin (2) were prepared as stable yellow crystalline compounds, which are the cyclic analogues of electron-donating hexaarylbutadienes. Upon two-electron oxidation, they are reversibly transformed into the title dications (1 2 + and 2 2 + ) exhibiting near-infrared (NIR) absorptions, which were also isolated as stable salts. These redox pairs can serve as new entries into less well-explored organic NIR-electrochromic systems, and the separation of redox peaks (electrochemical bistability) was attained for 1/ 1 2 + and 2/2 2 + , thanks to drastic geometrical changes between neutral and dicationic states, as revealed by a series of X-ray analyses. Thiepin-S,S-dioxide analogue (3/3 2 + ) exhibits quite similar dynamic redox behavior due to nonaromatic nature of the dibenzothiepin and -oxepin unit in 1 2 + and 2 2 + , whereas the thiepin-S-oxide derivative (4/4 2 + ) does not exhibit bistability due to the smaller change in geometry upon electron transfer, showing that a subtle change of a bridging atom in the central seven-membered ring can modify the redox properties.

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9,9'-Bi(xanthene)-Type Hexaphenylethane Derivatives as Advanced Organic Electrochromic Systems

Cited by 7 publications

References 94 publications

Enantioselective Synthesis of Spirosilabicyclohexenes by Asymmetric Dual Ring Expansion of Spirosilabicyclobutane with Alkynes

Enantioselective Synthesis of Spirosilabicyclohexenes by Asymmetric Dual Ring Expansion of Spirosilabicyclobutane with Alkynes

Enantioselective Synthesis of Spirosilabicyclohexenes by Asymmetric Dual Ring Expansion of Spirosilabicyclobutane with Alkynes

Near‐Infrared Electrochromic Behavior of Dibenzothiepin Derivatives Attached with Two Michler's Hydrol Blue Units

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