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Spectroelectrochemical studies of the redox active tris4-(triazol-1-yl)phenylamine linker and redox state manipulation of Mn(ii)/Cu(ii) coordination frameworks

机译:氧化还原活性三4-(三唑-1-基)苯基胺连接子的光谱电化学研究及Mn(ii)/Cu(ii)配位框架的氧化还原态操纵

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摘要

This work describes the successful incorporation of a redox active linker, tris(4-(1H-1,2,4-triazol-1-yl)phenyl)amine (TTPA) into Mn(ii)/Cu(ii) based coordination frameworks. Solution state in situ spectroelectrochemistry of EPR and UV/Vis/NIR of the TTPA ligand were measured to gain a deeper understanding of the charge delocalization of the triphenylamine backbone. The assignments of the absorption bands for the radical cations in UV/Vis/NIR spectroelectrochemistry were supported by DFT calculations. For Mn(ii)/Cu(ii) based coordination frameworks, solid state electrochemical and in situ spectroelectrochemical methods were applied to elucidate the accessible redox states and the optical properties of the frameworks. The findings provide a basic comprehension of the interconversion of different redox states and how an electroactive framework can be potentially used in applications of electrochromic and optical devices.
机译:这项工作描述了将氧化还原活性连接剂三(4-(1H-1,2,4-三唑-1-基)苯基)胺(TTPA)成功掺入基于Mn(ii)/Cu(ii)的配位框架中。测量了TTPA配体EPR和UV/Vis/NIR的溶液态原位光谱电化学,以更深入地了解三苯胺主链的电荷离域。DFT计算支持了UV/Vis/NIR光谱电化学中自由基阳离子吸收带的分配。对于基于Mn(ii)/Cu(ii)的配位框架,应用固态电化学和原位光谱电化学方法阐明了可及的氧化还原态和框架的光学性质。这些发现为不同氧化还原态的相互转换以及电活性框架如何潜在地用于电致变色和光学器件的应用提供了基本的理解。

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