Tunable Electronic Structure via DNA-Templated Heteroaggregates of Two Distinct Cyanine Dyes.
Tunable Electronic Structure via DNA-Templated Heteroaggregates of Two Distinct Cyanine Dyes.
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DOI：
10.1021/acs.jpcc.2c04336
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发表时间：
2022-10-13
影响因子：
3.7
通讯作者：
Pensack, Ryan D.
中科院分区：
文献类型：
--
作者：
Huff, Jonathan S.;Diaz, Sebastian A.;Barclay, Matthew S.;Chowdhury, Azhad U.;Chiriboga, Matthew;Ellis, Gregory A.;Mathur, Divita;Patten, Lance K.;Roy, Simon K.;Sup, Aaron;Biaggne, Austin;Rolczynski, Brian S.;Cunningham, Paul D.;Li, Lan;Lee, Jeunghoon;Davis, Paul H.;Yurke, Bernard;Knowlton, William B.;Medintz, Igor L.;Turner, Daniel B.;Melinger, Joseph S.;Pensack, Ryan D.
分子激子可用于光收集、有机光电子学和纳米级计算。电子能量转移（EET）是基于分子激子的器件功能的核心过程。实现高量子效率的EET是激子器件的常见障碍，通常是由于缺乏表现出有利光谱重叠的供体和受体分子。EET量子效率可以通过使用杂聚集体-化学上不同的染料的聚集体-而不是单独的染料作为能量中继单元来显著提高。然而，控制异质聚集体的组装仍然是一个重大的挑战。在这里，我们使用DNA霍利迪路口组装同源和异源四聚体聚集体的原型花青染料Cy 5和Cy5.5。除了允许控制聚集体中染料的数量之外，DNA模板化组装还赋予对聚集体组成的控制，即，组成Cy 5和Cy5.5染料的比例。通过改变Cy 5和Cy5.5的比例，我们表明，所得到的四聚体的最强烈的吸收特征可以在几乎200 meV（1600 cm-1）的范围内的能量转移。所有的四聚体包装在H-聚集体的形式，并表现出淬灭的发射和大幅减少的激发态寿命相比，单体染料。我们应用一个纯电子激子理论模型来描述所观察到的吸收光谱的进展。该模型与测量的数据和更复杂的振动模型的吸收和圆二色性光谱，表明Cy 5和Cy5.5杂聚集体在很大程度上描述了分子激子理论。最后，我们扩展了纯电子激子模型来描述一个理想化的J-聚集的基础上Förster共振能量转移（FRET），并讨论了这种设备的潜在优势，传统的FRET继电器。
Molecular excitons are useful for applications in light harvesting, organic optoelectronics, and nanoscale computing. Electronic energy transfer (EET) is a process central to the function of devices based on molecular excitons. Achieving EET with a high quantum efficiency is a common obstacle to excitonic devices, often owing to the lack of donor and acceptor molecules that exhibit favorable spectral overlap. EET quantum efficiencies may be substantially improved through the use of heteroaggregates—aggregates of chemically distinct dyes—rather than individual dyes as energy relay units. However, controlling the assembly of heteroaggregates remains a significant challenge. Here, we use DNA Holliday junctions to assemble homo- and heterotetramer aggregates of the prototypical cyanine dyes Cy5 and Cy5.5. In addition to permitting control over the number of dyes within an aggregate, DNA-templated assembly confers control over aggregate composition, i.e., the ratio of constituent Cy5 and Cy5.5 dyes. By varying the ratio of Cy5 and Cy5.5, we show that the most intense absorption feature of the resulting tetramer can be shifted in energy over a range of almost 200 meV (1600 cm–1). All tetramers pack in the form of H-aggregates and exhibit quenched emission and drastically reduced excited-state lifetimes compared to the monomeric dyes. We apply a purely electronic exciton theory model to describe the observed progression of the absorption spectra. This model agrees with both the measured data and a more sophisticated vibronic model of the absorption and circular dichroism spectra, indicating that Cy5 and Cy5.5 heteroaggregates are largely described by molecular exciton theory. Finally, we extend the purely electronic exciton model to describe an idealized J-aggregate based on Förster resonance energy transfer (FRET) and discuss the potential advantages of such a device over traditional FRET relays.
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对氰染料CY5的溶解性和电子特性的取代效应：密度功能和时间依赖性密度功能理论计算。
DOI：
10.3390/molecules26030524
发表时间：
2021-01-20
期刊：
Molecules (Basel, Switzerland)
影响因子：
--
作者：
Biaggne A;Knowlton WB;Yurke B;Lee J;Li L
通讯作者：
Li L
影响因子：
--
作者：
DICKE, RH
通讯作者：
DICKE, RH
影响因子：
23.5
作者：
Hart, Stephanie M.;Chen, Wei Jia;Schlau-Cohen, Gabriela S.
通讯作者：
Schlau-Cohen, Gabriela S.
影响因子：
3.7
作者：
Barclay, Matthew S.;Wilson, Christopher K.;Pensack, Ryan D.
通讯作者：
Pensack, Ryan D.
影响因子：
8.6
作者：
Fowler, Austin G.;Whiteside, Adam C.;Hollenberg, Lloyd C. L.
通讯作者：
Hollenberg, Lloyd C. L.