State Key Lab for Advanced Metals and Materials, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing, 100083, P.R. China.
Chemistry. 2018 Dec 3;24(67):17756-17766. doi: 10.1002/chem.201803473. Epub 2018 Nov 7.
Photochromic diarylethene derivatives, which can reversibly switch the fluorescence of adjacent fluorophores between the ON and OFF states under light irradiation, have been widely used to construct photoswitchable materials. Herein, eight dithienylethene (DTE) groups are integrated onto one polyhedral oligomeric silsesquioxane (POSS) core, obtaining a novel super molecular photoswitch. After being doped into conjugated polymer nanoparticles, the POSS-DTE molecules show a higher contrast on/off photoswitching performance and a quicker responsive speed than free DTE molecules at same molar concentration of photochromic units. This enhanced photoswitching efficiency is attributed to the increased molecular interaction of the ring-open form and lowered energy of the ring-closed form of the DTE units on the POSS core, which is beneficial for the ring-closing reaction and subsequent energy transfer between photoswitch and fluorophores. In addition, POSS-DTE also exhibits good photomodulation behavior in the conjugated polymer film, giving it potential applications in optical devices.
螺环二噻吩乙烯衍生物在光照射下可以可逆地将相邻荧光团的荧光在开态和关态之间切换,因此被广泛用于构建光致变色材料。在此,将八个二噻吩乙烯(DTE)基团集成到一个多面体低聚倍半硅氧烷(POSS)核上,得到了一种新型的超分子光开关。将 POSS-DTE 分子掺杂到共轭聚合物纳米粒子中后,与相同摩尔浓度的光致变色单元的游离 DTE 分子相比,POSS-DTE 分子表现出更高的对比度开/关光致变色性能和更快的响应速度。这种增强的光致变色效率归因于 POSS 核上 DTE 单元的开环形式的分子相互作用增加和闭环形式的能量降低,这有利于环封闭反应和随后光开关和荧光团之间的能量转移。此外,POSS-DTE 在共轭聚合物膜中也表现出良好的光调制行为,使其在光学器件中有潜在的应用。