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揭示支化低聚芴的分子结构与双光子吸收特性之间的关系。

Unveiling the molecular structure and two-photon absorption properties relationship of branched oligofluorenes.

作者信息

Zucolotto Cocca Leandro H, Pelosi André Gasparotto, Abegão Luis M G, de Q Garcia Rafael, Mulatier Jean-Christophe, Pitrat Delphine, Barsu Cyrille, Andraud Chantal, Mendonça Cleber R, Vivas Marcelo G, De Boni Leonardo

机构信息

Photonics Group, Instituto de Física de São Carlos, Universidade de São Paulo, CP 369, 13560-970 São Carlos, SP, Brazil.

Grupo de Fotônica, Instituto de Física, Universidade Federal de Goiás, Goiânia, 74690-900, GO, Brazil.

出版信息

Phys Chem Chem Phys. 2023 Feb 8;25(6):5021-5028. doi: 10.1039/d2cp05189c.

Abstract

Organic molecules have been intensively studied during the last few decades because of their photonics and biological applications. In this material class, the fluorene molecules present outstanding optical features, for example, high values of two-photon absorption (2PA) cross-sections, visible transparency, and high fluorescence quantum yield. Also, it is possible to improve the nonlinear optical response by modifying the fluorene molecular structure. In this context, herein, we have synthesized V and Y-shaped branching oligofluorenes containing two and three fluorene moieties in each branch. Such a molecular strategy may exponentially enhance the nonlinear optical response due to the coherent coupling among the molecular arms. Thus, we combined the use of femtosecond Z-scan spectroscopy and white light transient absorption spectroscopy (TAS) to understand the molecular structure and 2PA property relationship of branching oligofluorenes. The results show that there is a universal relationship between the 2PA cross-section and the effective π-electron number () given by (GM) = (079 ± 0.03), which is independent of the molecular shape (linear, V or Y-shaped). Therefore, the intramolecular charge transfer responsible for the cooperative effect among the branches does not occur. This statement is corroborated by the results of the femtosecond TAS technique.

摘要

在过去几十年中,由于有机分子在光子学和生物学方面的应用,它们受到了广泛研究。在这类材料中,芴分子具有出色的光学特性,例如,双光子吸收(2PA)截面值高、可见光透明度高以及荧光量子产率高。此外,通过修饰芴分子结构可以改善其非线性光学响应。在此背景下,我们合成了在每个分支中含有两个和三个芴部分的V形和Y形支化低聚芴。这种分子策略可能会由于分子臂之间的相干耦合而指数级增强非线性光学响应。因此,我们结合使用飞秒Z扫描光谱和白光瞬态吸收光谱(TAS)来理解支化低聚芴的分子结构与2PA性质之间的关系。结果表明,2PA截面与有效π电子数()之间存在普遍关系,由(GM) = (079 ± 0.03)给出,这与分子形状(线性、V形或Y形)无关。因此,负责分支之间协同效应的分子内电荷转移并未发生。飞秒TAS技术的结果证实了这一说法。

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