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侧基如何决定钙钛矿-罗丹明光收集组件中的能量和电子转移

How Pendant Groups Dictate Energy and Electron Transfer in Perovskite-Rhodamine Light Harvesting Assemblies.

作者信息

DuBose Jeffrey T, Kamat Prashant V

机构信息

Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556, United States.

Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States.

出版信息

J Am Chem Soc. 2023 Mar 1;145(8):4601-4612. doi: 10.1021/jacs.2c12248. Epub 2023 Feb 16.

Abstract

Energy and electron transfer processes allow for efficient manipulation of excited states within light harvesting assemblies for photocatalytic and optoelectronic applications. We have now successfully probed the influence of acceptor pendant group functionalization on the energy and electron transfer between CsPbBr perovskite nanocrystals and three rhodamine-based acceptor molecules. The three acceptors─rhodamine B (RhB), rhodamine isothiocyanate (RhB-NCS), and rose Bengal (RoseB)─contain an increasing degree of pendant group functionalization that affects their native excited state properties. When interacting with CsPbBr as an energy donor, photoluminescence excitation spectroscopy reveals that singlet energy transfer occurs with all three acceptors. However, the acceptor functionalization directly influences several key parameters that dictate the excited state interactions. For example, RoseB binds to the nanocrystal surface with an apparent association constant ( = 9.4 × 10 M) 200 times greater than RhB ( = 0.05 × 10 M), thus influencing the rate of energy transfer. Femtosecond transient absorption reveals the observed rate constant of singlet energy transfer (k) is an order-of-magnitude greater for RoseB ( = 1 × 10 s) than for RhB and RhB-NCS. In addition to energy transfer, each acceptor had a subpopulation of molecules (∼30%) that underwent electron transfer as a competing pathway. Thus, the structural influence of acceptor moieties must be considered for both excited state energy and electron transfer in nanocrystal-molecular hybrids. The competition between electron and energy transfer further highlights the complexity of excited state interactions in nanocrystal-molecular complexes and the need for careful spectroscopic analysis to elucidate competitive pathways.

摘要

能量和电子转移过程能够有效地操控光捕获组件内的激发态,以用于光催化和光电应用。我们现已成功探究了受体侧基官能化对CsPbBr钙钛矿纳米晶体与三种罗丹明基受体分子之间能量和电子转移的影响。这三种受体——罗丹明B(RhB)、异硫氰酸罗丹明(RhB-NCS)和孟加拉玫瑰红(RoseB)——的侧基官能化程度不断增加,这影响了它们的本征激发态性质。当与作为能量供体的CsPbBr相互作用时,光致发光激发光谱表明,所有三种受体都发生了单重态能量转移。然而,受体官能化直接影响了几个决定激发态相互作用的关键参数。例如,RoseB以表观缔合常数( = 9.4 × 10 M)与纳米晶体表面结合,比RhB( = 0.05 × 10 M)大200倍,从而影响能量转移速率。飞秒瞬态吸收表明,RoseB的单重态能量转移观测速率常数(k)( = 1 × 10 s)比RhB和RhB-NCS大一个数量级。除了能量转移外,每种受体都有一部分分子(约30%)作为竞争途径发生了电子转移。因此,对于纳米晶体 - 分子杂化物中的激发态能量和电子转移,都必须考虑受体部分的结构影响。电子转移和能量转移之间的竞争进一步凸显了纳米晶体 - 分子复合物中激发态相互作用的复杂性,以及进行仔细光谱分析以阐明竞争途径的必要性。

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