School of Chemistry and Chemical Engineering, Nantong University, Nantong 226019, China.
School of Chemistry and Chemical Engineering, Nantong University, Nantong 226019, China.
J Colloid Interface Sci. 2023 Jul;641:803-811. doi: 10.1016/j.jcis.2023.03.109. Epub 2023 Mar 22.
A novel water-soluble phosphate-pillar[5]arene (WPP5)-based artificial light-harvesting system (LHS) was successfully fabricated through the supramolecular assembly of phenyl-pyridyl-acrylonitrile derivative (PBT), WPP5, and organic pigment Eosin Y (ESY). Initially, after host-guest interaction, WPP5 could bind well with PBT and form WPP5 ⊃ PBT complexes in water, which further assembled into WPP5 ⊃ PBT nanoparticles. WPP5 ⊃ PBT nanoparticles performed an outstanding aggregation-induced emission (AIE) capability because of the J-aggregates of PBT in WPP5 ⊃ PBT nanoparticles, which were appropriate as fluorescence resonance energy transfer (FRET) donors for artificial light-harvesting. Moreover, due to the emission region of WPP5 ⊃ PBT overlapped well with the UV-Vis absorption of ESY, the energy of WPP5 ⊃ PBT (donor) could be significantly transferred to ESY (acceptor) via FRET process in WPP5 ⊃ PBT-ESY nanoparticles. Notably, the antenna effect (AE) of WPP5 ⊃ PBT-ESY LHS was determined to be 30.3, which was much higher than that of recent artificial LHSs for photocatalytic cross-coupling dehydrogenation (CCD) reactions, suggesting a potential application in photocatalytic reaction. Furthermore, through the energy transfer from PBT to ESY, the absolute fluorescence quantum yields performed a remarkable increase from 14.4% (for WPP5 ⊃ PBT) to 35.7% (for WPP5 ⊃ PBT-ESY), further confirming their FRET processes in WPP5 ⊃ PBT-ESY LHS. Subsequently, in order to output the harvested energy for catalytic reactions, WPP5 ⊃ PBT-ESY LHSs were used as photosensitizers to catalyze the CCD reaction of benzothiazole and diphenylphosphine oxide. Compared to free ESY group (21%), a significant cross-coupling yield of 75% in WPP5 ⊃ PBT-ESY LHS was observed, because more UV region energy of PBT was transferred to ESY for CCD reaction, which suggested more potential in improving the catalytic activity of organic pigment photosensitizers in aqueous systems.
通过超分子组装苯并吡啶丙烯腈衍生物（PBT）、水溶性磷桥[5]芳烃（WPP5）和有机颜料曙红 Y（ESY），成功制备了一种新型水溶性磷桥[5]芳烃（WPP5）基人工光捕获系统（LHS）。最初，在主客体相互作用后，WPP5 可以与 PBT 很好地结合，并在水中形成 WPP5⊃PBT 配合物，进一步组装成 WPP5⊃PBT 纳米颗粒。WPP5⊃PBT 纳米颗粒表现出出色的聚集诱导发射（AIE）性能，因为 PBT 在 WPP5⊃PBT 纳米颗粒中的 J-聚集体，可作为人工光捕获的荧光共振能量转移（FRET）供体。此外，由于 WPP5⊃PBT 纳米颗粒中 PBT 的发射区域与 ESY 的紫外-可见吸收区域很好地重叠，因此 WPP5⊃PBT（供体）的能量可以通过 FRET 过程显著转移到 ESY（受体）中在 WPP5⊃PBT-ESY 纳米颗粒中。值得注意的是，WPP5⊃PBT-ESY LHS 的天线效应（AE）被确定为 30.3，远高于最近用于光催化交叉偶联脱氢（CCD）反应的人工 LHS，表明其在光催化反应中具有潜在的应用。此外，通过 PBT 向 ESY 的能量转移，绝对荧光量子产率从 14.4%（对于 WPP5⊃PBT）显著增加到 35.7%（对于 WPP5⊃PBT-ESY），进一步证实了它们在 WPP5⊃PBT-ESY LHS 中的 FRET 过程。随后，为了输出用于催化反应的收集能量，WPP5⊃PBT-ESY LHS 被用作光催化剂来催化苯并噻唑和二苯膦氧化物的 CCD 反应。与游离 ESY 组（21%）相比，在 WPP5⊃PBT-ESY LHS 中观察到显著的交叉偶联产率为 75%，因为 PBT 的更多 UV 区域能量被转移到 ESY 用于 CCD 反应，这表明在提高有机颜料光催化剂在水相中的催化活性方面具有更大的潜力。
