Fluence-Dependent Photoinduced Charge Transfer Dynamics in Polymer-Wrapped Semiconducting Single-Walled Carbon Nanotubes.

IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Journal of the American Chemical Society Pub Date : 2024-11-13 Epub Date: 2024-10-31 DOI:10.1021/jacs.4c11118
Zachary X W Widel, James A Alatis, Riley H Stephenson, Francesco Mastrocinque, Alexander C Wilcox, George Bullard, Jean-Hubert Olivier, Yusong Bai, Peng Zhang, David N Beratan, Michael J Therien
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Abstract

Because an individual single-walled carbon nanotube (SWNT) can absorb multiple photons, the exciton density within a single tube depends upon excitation conditions. In SWNT-based energy conversion systems, interactions between excitons and charges make it possible for multiple types of charge transfer reactions. We exploit a SWNT-molecular donor-acceptor hybrid system (R-PBN(b)-Ph6-PDI-[(6,5) SWNT]) that fixes spatial organization and stoichiometry of perylene diimide (PDI) electron acceptors on the nanotube surface, to elucidate how excitation fluence affects ultrafast charge separation (CS) and the nature of charge recombination (CR) dynamics triggered upon SWNT near-infrared excitation. Pump-probe data characterizing these photoinduced CS and thermal CR reactions were acquired over excitation fluences that produce ∼5-125 excitons per 700 nm long nanotube. These experiments show that optical excitation gives rise to CS states in which PDI radical anions (PDI-•) and SWNT hole polarons (SWNT•+) have geminate and nongeminate spatial relationships. Under low excitation fluences, the observed dynamics reflect CR reactions of these geminate and nongeminate CS states. As excitation fluence increases, persistent excitons, which have not undergone CS, undergo reaction with ([SWNT(•+)n]-(PDI-•)n) CS states to produce lower-energy CS states that are characterized by hole (SWNT•+) and electron (SWNT•-) polarons. When nongeminate SWNT•+ and SWNT•- charge carriers are generated, CR dynamics depend on the time scale required for these oppositely charged solvated SWNT polarons to encounter each other. Because SWNT excitons have substantial excited-state reduction (1E-/*) and excited-state oxidation (1E*/+) potentials, they can drive additional charge transfer reactions involving initially prepared CS states under experimental conditions where excess excitons are present.

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聚合物包裹的半导体单壁碳纳米管中的光诱导电荷转移动力学。
由于单根单壁碳纳米管(SWNT)可以吸收多个光子,因此单根管内的激子密度取决于激发条件。在基于 SWNT 的能量转换系统中,激子与电荷之间的相互作用使多种类型的电荷转移反应成为可能。我们利用一种固定了纳米管表面过二亚胺(PDI)电子受体的空间组织和化学计量的 SWNT 分子供体-受体混合系统(R-PBN(b)-Ph6-PDI-[(6,5) SWNT]),来阐明激发通量如何影响超快电荷分离(CS)以及 SWNT 近红外激发时引发的电荷重组(CR)动力学的性质。在每根 700 nm 长的纳米管产生 ∼5-125 个激子的激发通量下,获得了表征这些光诱导 CS 和热 CR 反应的泵探数据。这些实验表明,光激发产生的 CS 状态中,PDI 自由基阴离子(PDI--)和 SWNT 空穴极子(SWNT-+)具有宝石状和非宝石状空间关系。在低激发通量下,观察到的动态反映了这些基态和非基态 CS 状态的 CR 反应。随着激发通量的增加,未发生 CS 反应的持久激子与([SWNT(-+)n]-(PDI--)n)CS 态发生反应,产生以空穴(SWNT-+)和电子(SWNT--)极子为特征的低能 CS 态。当非纯化的 SWNT-+ 和 SWNT-- 电荷载流子产生时,CR 动态取决于这些带相反电荷的溶解 SWNT 极子相互相遇所需的时间尺度。由于 SWNT 激子具有很大的激发态还原(1E-/*)和激发态氧化(1E*/+)电势,因此在存在过量激子的实验条件下,它们可以驱动涉及最初制备的 CS 态的额外电荷转移反应。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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