Long-distance electronic coupling in diferrocenyl compounds with cross-conjugated <ce:italic>germinal</ce:italic>-diethynylethene bridges

Yang Fan; Hua-Min Li; Guo-Dong Zou; Xu Zhang; Meng Li; Jia-Hui Wu; Xin Zhang; Hai-Ting Lu

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Long-distance electronic coupling in diferrocenyl compounds with cross-conjugated germinal-diethynylethene bridges

机译：脱洛苯基化合物中的长距离电子耦合，具有交叉共轭发芽 - 二烯基乙烯桥

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A series ofgerminal-diethynylethene (gem-DEE) bridged diferrocenyl compounds, including 1,1-[bis(ferrocenylethynyl)methylene]cyclohexane (1), 1,1-[bis(ferrocenylethynyl)methylene]tetrahydro-2H-pyran (2), and 1,1-[bis(ferrocenylethynyl)methylene]tetrahydro-2H-thiopyran (3) were synthesized and characterized. The Fe?Fe distance between the two ferrocenyl termini reaches up to ～9?? for compounds2and3. The electrochemical measurements demonstrate moderate electronic coupling between thegem-DEE-bridged ferrocenyl (Fc) termini in this cross-conjugated system. UV–vis–NIR spectroscopy studies suggest that the monocation species of these compounds belong to class II mixed-valence systems in Robin–Day classification. DFT calculations further reveal electronic structures of these cross-conjugated diferrocenyl compounds.

机译：一系列碳邻乙烯基乙烯（GEM-DEE）桥接脱苯基化合物，包括1,1- [双（二茂铁乙炔基）亚甲基]环己烷（1），1,1- [双（二茂铁乙炔基）亚甲基]四氢-2H-吡喃（2）合成和表征1,1- [双（二氯环酰乙炔基）亚甲基]四氢-2H-硫嘧啶（3）。两种二茂铁末端之间的Fe距离达到〜9 ?? 用于化合物2和3。电化学测量在该交叉共轭系统中展示了在该交叉共轭系统中的可见德桥桥桥（FC）末端之间的中等电子耦合。 UV-Vis-Nir光谱研究表明，这些化合物的单位分配属于Robin日分类中的II类混合价系统。 DFT计算进一步揭示了这些交叉缀合的脱盐苯基化合物的电子结构。

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来源
《Journal of Organometallic Chemistry》 |2018年第2018期|共7页
作者
Yang Fan; Hua-Min Li; Guo-Dong Zou; Xu Zhang; Meng Li; Jia-Hui Wu; Xin Zhang; Hai-Ting Lu;
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作者单位

College of Chemistry and Chemical Engineering Xinyang Normal University;

College of Chemistry and Chemical Engineering Xinyang Normal University;

College of Chemistry and Chemical Engineering Xinyang Normal University;

Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences;

College of Chemistry and Chemical Engineering Xinyang Normal University;

College of Chemistry and Chemical Engineering Xinyang Normal University;

College of Chemistry and Chemical Engineering Xinyang Normal University;

College of Chemistry and Chemical Engineering Xinyang Normal University;

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原文格式 PDF
正文语种 eng
中图分类元素有机化合物;
关键词
Diferrocenyl; Diethynylethene; Cross-conjugated; Electronic coupling; Mixed-valence;

机译：Dirercenyl;乙酰烯基乙烯;交叉共轭;电子耦合;混合效价;

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2. Diferrocenes Bridged by a Geminal Diethynylethene Scaffold with Varying Pendant Substituents: Electronic Interactions in Cross-Conjugated System [J] . Fan Yang, Li Hua-Min, Zou Guo-Dong, Organometallics . 2017,第21期

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Long-distance electronic coupling in diferrocenyl compounds with cross-conjugated germinal-diethynylethene bridges

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