Concentration-dependent photophysical switching in mixed self-assembled monolayers of pentacene and perylenediimide on gold nanoclusters†,Physical Chemistry Chemical Physics

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Concentration-dependent photophysical switching in mixed self-assembled monolayers of pentacene and perylenediimide on gold nanoclusters†
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2018-02-27 00:00:00 , DOI: 10.1039/c8cp00174j
Daiki Kato _{1,

2,

3,

4,

5} , Hayato Sakai _{1,

2,

3,

4,

5} , Yasuyuki Araki _{5,

6,

7,

8} , Takehiko Wada _{5,

6,

7,

8} , Nikolai V. Tkachenko _{9,

10,

11,

12} , Taku Hasobe _{1,

2,

3,

4,

5}

Affiliation

Photophysical control and switching on organic–inorganic hybrid interfaces are of great interest in diverse fundamental and applicative research areas. 6,13-Bis(triisopropylsilylethynyl)pentacene (TP) is well-known to exhibit efficient singlet fission (SF) for generation of high-yield triplet excited states in aggregated forms, whereas perylenediimide (PDI) ensembles show the characteristic excimer formation. Additionally, a combination of pentacene (electron donor: D) and PDI (electron acceptor: A) is expected to undergo an efficient photoinduced electron transfer (PET), and absorption of two chromophores combined covers the entire visible region. Therefore, the concentration-dependent mixed self-assembled monolayers (SAMs) composed of two chromophores enable us to control and switch the photophysical processes on a surface. In this work, a series of mixed SAMs composed of TP and PDI units on gold nanoclusters (GNCs) were newly synthesized by changing the relative molecular concentration ratios. Structural control of mixed SAMs on a gold surface based on the concentration ratios was successfully achieved. Time-resolved femtosecond and nanosecond transient absorption measurements clearly demonstrate photophysical control and switching of the above competitive reactions such as SF, electron transfer (ET) and excimer formation. The maximum quantum yields of triplet states (Φ_T = ∼170%) and electron transfer (Φ_ET = ∼95%) were quantitatively evaluated by changing the concentration ratios. The rate constants of SF and excimer processes are largely dependent on the concentration ratios, whereas the rate constants of ET processes approximately remain constant. These findings are also discussed based on the statistical framework of the assembly of chromophores on the gold surface.

中文翻译：

并五苯和per二酰亚胺混合自组装单分子膜在金纳米簇上的浓度依赖性光物理转换†

在各种基础和应用研究领域中，光物理控制和有机-无机混合界面的切换都引起了人们的极大兴趣。众所周知，6,13-双（三异丙基甲硅烷基乙炔基）并五苯（TP）表现出有效的单重裂变（SF），可用于以聚集形式生成高产率的三重态激发态，而im二酰亚胺（PDI）团簇则表现出特征性的准分子形成。另外，并五苯（电子供体：D）和PDI（电子受体：A）的组合有望进行有效的光致电子转移（PET），并且两种发色团的吸收覆盖了整个可见光区域。因此，由两个生色团组成的浓度依赖性混合自组装单分子层（SAM）使我们能够控制和切换表面上的光物理过程。在这项工作中，通过改变相对分子浓度比，新合成了一系列由TP和PDI单元组成的金纳米团簇（GNC）上的混合SAM。成功实现了基于浓度比的金表面混合SAM的结构控制。时间分辨的飞秒和纳秒瞬态吸收测量清楚地证明了光物理控制和上述竞争性反应（如SF，电子转移（ET）和受激准分子形成）的切换。三重态的最大量子产率（时间分辨的飞秒和纳秒瞬态吸收测量清楚地证明了光物理控制和上述竞争性反应（如SF，电子转移（ET）和受激准分子形成）的切换。三重态的最大量子产率（时间分辨的飞秒和纳秒瞬态吸收测量清楚地证明了光物理控制和上述竞争性反应（如SF，电子转移（ET）和受激准分子形成）的切换。三重态的最大量子产率（Φ _Ť =〜170％）和电子转移（Φ _ET =约95％）进行定量，通过改变浓度比进行评价。SF和准分子过程的速率常数在很大程度上取决于浓度比，而ET过程的速率常数大致保持恒定。还基于金表面上生色团组装的统计框架讨论了这些发现。

更新日期：2018-02-27

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