Exploring the design of superradiant J-aggregates from amphiphilic monomer units
Exploring the design of superradiant J-aggregates from amphiphilic monomer units
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DOI：
10.1039/d2nr05747f
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发表时间：
2023-01-27
期刊：
影响因子：
6.7
通讯作者：
Caram, Justin R.
中科院分区：
文献类型：
--
作者：
Bailey, Austin D.;Deshmukh, Arundhati P.;Caram, Justin R.
激子发色团聚集体在成像和能量收集等领域具有广泛的适用性;然而，它们的合理设计需要使自组装原理适应激发态耦合的要求。使用良好的研究两亲性菁染料C8 S3作为模板，已知组装成管状激子聚集体，我们合成了几个红移的变体，并研究其自组装和physics。新的五甲川染料保持其管状自组装，并表现出几乎相同的红移和线形以及近红外波长。然而，详细的光物理分析发现，新的聚集体显示出显着的超辐射下降。此外，低温透射电镜显示，这些聚集体很容易形成短束的纳米管，其半径几乎是其三次甲基比较物的一半。我们采用计算筛选来获得关于这些新聚集体的结构成分如何影响其激子态的直觉，发现较窄的管能够组装成更多的排列，从而产生具有高度相似的红移程度的更无序的聚集体（即更少的超辐射）。
Excitonic chromophore aggregates have wide-ranging applicability in fields such as imaging and energy harvesting; however their rational design requires adapting principles of self-assembly to the requirements of excited state coupling. Using the well-studied amphiphilic cyanine dye C8S3 as a template-known to assemble into tubular excitonic aggregates-we synthesize several redshifted variants and study their self-assembly and photophysics. The new pentamethine dyes retain their tubular self-assembly and demonstrate nearly identical bathochromic shifts and lineshapes well into near-infrared wavelengths. However, detailed photophysical analysis finds that the new aggregates show a significant decline in superradiance. Additionally, cryo-TEM reveals that these aggregates readily form short bundles of nanotubes that have nearly half the radii of their trimethine comparators. We employ computational screening to gain intuition on how the structural components of these new aggregates affect their excitonic states, finding that the narrower tubes are able to assemble into a larger number of arrangements, resulting in more disordered aggregates (i.e. less superradiant) with highly similar degrees of redshift.