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Chalcogenoviologens: Versatile Building Blocks with Narrow Bandgap and Multiple Redox Center
Hits:    Update:2018/3/26 17:29:05

Viologen is a cationic organic molecule with excellent redox characteristics, which can undergo two-step reversible single electron redox with obvious color changes via applied voltage or direct illumination. In addition, viologen can effectively participate metal coordination and have developed rapidly in fields such as electrochromic display devices (ECD), metallosupramolecular assemblies, host-guest complexes, solar-to-fuel conversion, energy storage and many other utilities. However, the drawbacks such as low conjugation and large energy gap greatly limited the application of viologen derivatives in the field of solar energy conversion and energy storage.



To solve the problems mentioned above, Prof. Gang He’s group at Frontier Institute of Science and Technology (XJTU), has successfully introduced chalcogen atoms (S, Se, Te) into viologen and prepared chalcogen atoms-containing viologens which were named as “Chalcogenoviologens”. The new research found that chalcogenoviologens have the following characteristics: (1) the incorporation of the chalcogen-bridged group resulted in planar rigid backbone; (2) extra redox centres, except for reduction events of radical cation (E-RV+?) and the neutral species (E-RV). (3) reduced HOMO–LUMO gap (as low as 2.33 eV) with almost the same lower LUMO levels and redshift optical absorption in visible region. The solution-based/gel-based ECD were fabricated successfully and the water-soluble Se-BnV2+ and Te-BnV2+ were first used as both a photosensitizer and as an electron mediator for visible-light-driven hydrogen evolution due to their high visible light absorption and optimal energy levels, which provide a new strategy for developing organic photocatalysts. This not only greatly simplifies visible-light-driven hydrogen evolution system, but also greatly improves the efficiency of visible light catalysis. This result has been published in Angewandte Chemie International Edition, an authoritative journal of international chemistry (IF = 11.994), the title was “Narrow Band Gap Chalcogenoviologens for Electrochromism and Visible-Light-Driven Hydrogen Evolution”. Guoping Li, a PhD candidate from FIST, XJTU was the first author of this paper, XJTU was the only correspondent unit. This is also another important breakthrough in the field of chalcogen atoms-containing heterocyclic aromatic after 2017 (Angew. Chem. Int. Ed. 2017, 56, 15334-15338).

This work was supported by the Natural Science Foundation of China,  the Cyrus Chung Ying Tang Foundation, start funding from Xi’an Jiaotong University and Instrument Analysis Center of Xi’an Jiaotong University.

Paper Link: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201711761

Prof. Gang He’s group engages in the research of synthesis of main group elements-containing heterocycles and polymers and application in smart material, photocatalysis, organic battery and photodynamic antibacterial. Welcome students from relevant departments.

Homepage of Prof. Gang He’s research group: http://gr.xjtu.edu.cn/web/ganghe

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