Poly-p-hydroquinone Ethers: Isoenergetic Molecular Wires with Length-Invariant Oxidation Potentials and Cation Radical Excitation Energies,Journal of the American Chemical Society

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Poly-p-hydroquinone Ethers: Isoenergetic Molecular Wires with Length-Invariant Oxidation Potentials and Cation Radical Excitation Energies
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-03-16 , DOI: 10.1021/jacs.7b01226
Maxim V. Ivanov ₁ , Vincent J. Chebny ₁ , Marat R. Talipov ₁ , Rajendra Rathore ₁

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Typical poly-p-phenylene wires are characterized by strong interchromophoric electronic coupling with redox and optical properties being highly length-dependent. Herein we show that an incorporation of a pair of para-methoxy groups at each p-phenylene unit in poly-p-phenylene wires (i.e., PHEn) changes the nodal structure of HOMO that leads to length-invariant oxidation potentials and cation radical excitation energies. As such, PHEn represents a unique class of isoenergetic wires where hole delocalization mainly occurs via dynamic hopping and thus may serve as an efficient medium for long-range charge transfer. Availability of these wires will allow demonstration of long-range electron transfer via incoherent hopping using donor-bridge-acceptor systems with isoenergetic PHEn-based wires as bridges.

中文翻译：

聚对氢醌醚：具有长度不变氧化电位和阳离子自由基激发能的等能分子线

典型的聚对苯撑线的特点是强发色团间电子耦合，氧化还原和光学特性高度依赖于长度。在此，我们表明在聚对亚苯基线（即 PHEn）中的每个对亚苯基单元处引入一对对甲氧基会改变 HOMO 的节点结构，从而导致长度不变的氧化电位和阳离子自由基激发能量。因此，PHEn 代表了一类独特的等能线，其中空穴离域主要通过动态跳跃发生，因此可以作为长距离电荷转移的有效介质。这些导线的可用性将允许使用供体 - 桥 - 受体系统以等能基于 PHEn 的导线作为桥梁，通过非相干跳跃来演示远程电子转移。

更新日期：2017-03-16

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