<br>全顺式和全反式聚对亚苯基亚乙烯基的线性和非线性光学性质,The Journal of Physical Chemistry C

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全顺式和全反式聚对亚苯基亚乙烯基的线性和非线性光学性质
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2024-02-02 , DOI: 10.1021/acs.jpcc.3c07082
Haraprasad Mandal ₁ , Olusayo J Ogunyemi ₂ , Jake L Nicholson ₃ , Meghan E Orr ₁ , Remy F Lalisse ₃ , Ángel Rentería-Gómez ₃ , Achyut R Gogoi ₃ , Osvaldo Gutierrez ₃ , Quentin Michaudel _{3,

4} , Theodore Goodson _{1,

2}

Affiliation

聚对亚苯基亚乙烯基 (PPV) 是共轭聚合物家族的主要成分，具有理想的光电特性，适用于发光二极管 (LED) 和光伏器件等应用。尽管烯烃几何形状对 PPV 稳态光学性质的重大影响已被广泛研究，但具有精确立体化学的 PPV 尚未使用用于量子传感的非线性光谱以及用于生物应用的光捕获进行研究。在此，我们报告了通过合成全顺式和全反式PPV 共聚物，研究烯烃立体化学对线性和非线性光学性质的影响。我们使用经典光源和纠缠光源进行双光子吸收（TPA），并比较了这些立体定义的 PPV 的经典 TPA 和纠缠双光子吸收（ETPA）横截面。尽管全反式 PPV 的 TPA 截面预期高于全顺式PPV，可能是因为过渡偶极矩较大，但通过 ETPA 测量到了相反的趋势，全顺式PPV 表现出最高的 ETPA 截面部分。 DFT 计算表明，这种差异可能源于全顺式PPV 变体中纠缠光子与较低电子态的相互作用。此外，我们通过时间分辨荧光上转换和飞秒瞬态吸收技术探索了顺式和反式PPV 的光诱导过程。这项研究表明，PPV 在双光子吸收中的敏感性随经典光与量子光的变化而变化，并且可以通过控制重复烯烃的几何形状进行调制，这是其在量子传感、生物成像和生物医学领域应用的关键垫脚石。基于聚合物的光采集系统的设计。

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Linear and Nonlinear Optical Properties of All-cis and All-trans Poly(p-phenylenevinylene)

Poly(p-phenylenevinylene) (PPV) is a staple of the family of conjugated polymers with desirable optoelectronic properties for applications including light-emitting diodes (LEDs) and photovoltaic devices. Although the significant impact of olefin geometry on the steady-state optical properties of PPVs has been extensively studied, PPVs with precise stereochemistry have yet to be investigated using nonlinear optical spectroscopy for quantum sensing, as well as light harvesting for biological applications. Herein, we report our investigation of the influence of olefin stereochemistry on both linear and nonlinear optical properties through the synthesis of all-cis and all-trans PPV copolymers. We performed two-photon absorption (TPA) using a classical and entangled light source and compared both classical TPA and entangled two-photon absorption (ETPA) cross sections of these stereodefined PPVs. Whereas the TPA cross section of the all-trans PPV was expectedly higher than that of all-cis PPV, presumably because of the larger transition dipole moment, the opposite trend was measured via ETPA, with the all-cis PPV exhibiting the highest ETPA cross section. DFT calculations suggest that this difference might stem from the interaction of entangled photons with lower-lying electronic states in the all-cis PPV variant. Additionally, we explored the photoinduced processes for both cis and trans PPVs through time-resolved fluorescence upconversion and femtosecond transient absorption techniques. This study revealed that the sensitivity of PPVs in two-photon absorption varies with classical versus quantum light and can be modulated through the control of the geometry of the repeating alkenes, which is a key stepping stone toward their use in quantum sensing, bioimaging, and the design of polymer-based light-harvesting systems.

更新日期：2024-02-02

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