Enhancing Insulated Conjugated Polymer Fluorescence Quenching by Incorporating Dithia[3.3]paracyclophanes
Enhancing Insulated Conjugated Polymer Fluorescence Quenching by Incorporating Dithia[3.3]paracyclophanes
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DOI：
10.1021/acs.macromol.1c00136
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发表时间：
2021-03-25
期刊：
影响因子：
5.5
通讯作者：
Gavvalapalli, Nagarjuna
中科院分区：
文献类型：
--
作者：
Lillis, Ryan;Thomas, Maximillian R.;Gavvalapalli, Nagarjuna
绝缘的聚酰亚胺共轭聚合物具有更高的化学稳定性、光稳定性、荧光量子产率、电致发光、溶解性和链内电荷传输。然而，由于pi面是绝缘的，受体分子对绝缘聚合物的荧光猝灭作用受到了显著的阻碍。光致电荷转移是放大荧光猝灭传感器和有机太阳能电池电荷产生的关键步骤之一。受神经细胞轴突髓鞘间隙的启发，我们合成了一系列含双硫[3.3]对环芳烃(PCP)的绝缘无规共聚物，以增强其与受体分子的荧光猝灭。随着二硫杂[3.3]对环番单体含量的增加，共聚物在红区的吸收增加，光致发光量子产率降低。30%共聚物的Stern-Volmer猝灭常数约为金刚烷均聚物的4.5倍。与对照聚合物的比较表明，PCP中的穿透空间耦合作用可能是PCP增强荧光猝灭的一个可能的原因，此外，PCP还减少了空间位阻。所开发的共聚物在不显著牺牲光诱导电荷转移的情况下结合了聚合物绝缘的优点，这将有助于进一步将其用作放大荧光猝灭传感器和有机太阳能电池。
Insulated pi-conjugated polymers exhibit enhanced chemical stability, photostability, fluorescence quantum yield, electroluminescence, solubility, and intrachain charge transport. However, insulated polymer fluorescence quenching by acceptor molecules is significantly hampered as the pi-face is insulated. Photoinduced charge transfer is one of the key steps in amplified fluorescence quenching sensors and organic solar cells for charge generation. Inspired by the myelin sheath gaps in nerve cell axons, herein, we synthesized a series of insulated random copolymers of adamantanocyclophane with an increasing percentage of dithia[3.3]paracyclophane (PCP) from 5 to 30% to enhance the insulated polymer fluorescence quenching with acceptor molecules. As the percentage of the dithia[3.3]paracyclophane monomer increases, the copolymers showed an increase in absorption in the red region of the spectrum and also the copolymers' photoluminescence quantum yield reduced. The Stern-Volmer quenching constant of the 30% copolymer is ca. 4.5 times higher than that of the adamantanocyclophane homopolymer. A comparison with the control polymers indicated that the through-space-coupled interactions in PCP could be a plausible reason for the enhanced fluorescence quenching in copolymers in addition to the reduced steric hindrance by PCP. The developed copolymers combine the advantages of polymer insulation without significantly sacrificing the photoinduced charge transfer, which will help further their applicability as amplified fluorescence quenching sensors and in organic solar cells.