Covalently Tethered Assemblies Improve Energetic Homogeneity and Exciton Transport in Organic Materials
Covalently Tethered Assemblies Improve Energetic Homogeneity and Exciton Transport in Organic Materials
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DOI：
10.1021/acsmaterialslett.4c00279
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发表时间：
2024-03
影响因子：
11.4
通讯作者：
Alexander J. King;Victor A. Paulino;Skyler R. Hollinbeck;Ifigeneia Tsironi;Jarek A. Maleszka;Jean-Hubert Oliv
中科院分区：
文献类型：
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作者：
Alexander J. King;Victor A. Paulino;Skyler R. Hollinbeck;Ifigeneia Tsironi;Jarek A. Maleszka;Jean-Hubert Oliv
结构和功能的异质性是弱的非共价相互作用的结果，直接从溶液前体的有机材料的形成。虽然溶液相组件的共价束缚提供了一个令人信服的策略，以提高分子间的秩序，这种束缚策略对形成的固态材料的影响仍然没有建立。这项工作使用泵浦-探测显微镜来比较激发态动力学薄膜制成的束缚苝酰亚胺组件，从非共价组装。平均而言，束缚膜表现出更快，更均匀的激发态寿命，更强，更均匀的分子间耦合一致。激发态扩散的光学测量结果表明，系留膜的传输速度比对照膜快75%。动力学蒙特卡罗模拟表明，减少网站充满活力的障碍是足以定量解释扩散系数的差异。这些结果有力地支持了共价束缚是一种很有前途的策略，以提高分子材料的结构和能量有序。
Structural and functional heterogeneity is a consequence of the weak noncovalent interactions that direct the formation of organic materials from solution precursors. While covalent tethering of solution-phase assemblies provides a compelling strategy to enhance intermolecular order, the effects of this tethering strategy on the formed solid-state materials remain unestablished. This work uses pump–probe microscopy to compare excited-state dynamics in thin films fabricated from tethered perylene bisimide assemblies to those fabricated from noncovalent assemblies. On average, tethered films exhibit faster and more homogeneous excited-state lifetimes, consistent with stronger and more uniform intermolecular coupling. Optical measurements of excited-state diffusion show that the tethered film has ∼75% faster transport than the control film. Kinetic Monte Carlo modeling suggests that the reduction of site energetic disorder is sufficient to quantitatively explain the difference in diffusion coefficients. These results provide strong support that covalent tethering is a promising strategy to enhance the structural and energetic ordering in molecular materials.