One-Step Direct Oxidation of Alkoxy to Ketone for Evaporable Fullerene-Fused Ketone as Efficient Electron-Transport Materials
One-Step Direct Oxidation of Alkoxy to Ketone for Evaporable Fullerene-Fused Ketone as Efficient Electron-Transport Materials
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DOI：
10.21203/rs.3.rs-131562/v1
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发表时间：
2021-01
期刊：
影响因子：
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通讯作者：
Hao-Sheng Lin;Yue Ma;R. Xiang;Sergei Manzhos;Il Jeon;S. Maruyama;Y. Matsuo
中科院分区：
文献类型：
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作者：
Hao-Sheng Lin;Yue Ma;R. Xiang;Sergei Manzhos;Il Jeon;S. Maruyama;Y. Matsuo
酮类化合物是一种广泛应用于电气和医疗材料设计的化合物，通常由醇类化合物通过氧化反应转化而成。然而，当醇被保护/功能化时，直接氧化策略实质上受到抑制。在这里，我们展示了一种高效的溴化铜在富勒烯垂饰的帮助下促进了烷氧基一步直接氧化成酮。机理研究揭示了富勒烯在烷氧基一步氧化成酮的过程中可以作为电子贫。在没有富勒烯吊坠的情况下，无法达到的活化能阈值阻碍了烷氧基的直接氧化。在富勒烯悬垂物存在的情况下，溴化铜氧化的富勒烯自由基阳离子可以激活邻近的烷氧基的C-H键，为引发烷氧基的直接氧化提供了有利的能垒。制备的富勒烯-熔融酮具有较高的热稳定性，提供了具有高电子迁移率的无针孔非晶电子传输层。
Ketones, one of widely applied moieties in designing electrical and medical materials, commonly converted from the alcohols through the oxidation reactions. However, when alcohols are protected/functionalized, the direct oxidation strategies are substantially curbed. Here we show a highly efficient copper bromide promoted one-step direct oxidation of alkoxy to ketone with the aid of a fullerene pendant. Mechanistic studies unveil that fullerene can serve as an electron poor proceeding the one-step oxidation of alkoxy group to ketone. In the absence of fullerene pendant, the unreachable activation energy threshold hampers the direct oxidation of alkoxy group. In the presence of fullerene pendant, copper bromide oxidized fullerene radical cation can activate neighboring C–H bond of alkoxy moieties, allowing a favorable energy barrier for initiating the direct oxidation of alkoxy group. Produced fullerene-fused ketone indicates high thermal stability, affording the pin-hole free and amorphous electron-transport layer with high electron-transport mobility.