Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, 1-1 Minami Osawa, Hachioji, Tokyo, 192-0376, Japan.
Angew Chem Int Ed Engl. 2017 May 2;56(19):5288-5293. doi: 10.1002/anie.201700466. Epub 2017 Mar 24.
A series of end-functionalized poly(9,9'-di-n-octylfluorene vinylene)s (EF-PFVs) with different end groups were obtained by 1) synthesizing EF-PFV with vinyl end groups by acyclic diene metathesis (ADMET) polymerization with a molybdenum catalyst and termination with an aldehyde and 2) subsequent olefin metathesis of the vinyl group with the molybdenum catalyst followed by Wittig-type coupling with another aldehyde. The exclusive formation of EF-PFVs containing a vinyl end group by the ADMET polymerization was confirmed by grafting PEG, and by the synthesis of amphiphilic triblock copolymers by combining atom transfer radical polymerization from the PFV chain end with PEG grafting through a click reaction. Various EF-PFVs with different end groups, such as C F , pyridyl, ferrocenyl, and terthiophene, have thus been prepared. Their fluorescence spectra (e.g., intensities, emission wavelengths) were influenced by the end groups and the length of the conjugation.
一系列具有不同端基的端官能化聚（9,9'-二正辛基芴基亚乙烯基）（EF-PFV）通过以下方法获得：1）通过具有钼催化剂的开环二烯复分解（ADMET）聚合合成具有乙烯基端基的 EF-PFV，并用醛终止，2）随后用钼催化剂使乙烯基进行烯烃复分解，然后用另一个醛进行Wittig 型偶联。通过接枝 PEG 以及通过通过点击反应将 PFV 链末端的原子转移自由基聚合与 PEG 接枝相结合来合成两亲性三嵌段共聚物，从而确认 ADMET 聚合生成仅含有乙烯基端基的 EF-PFV。因此，制备了各种具有不同端基的 EF-PFV，例如 CF 、吡啶基、二茂铁基和三噻吩基。它们的荧光光谱（例如强度、发射波长）受到端基和共轭长度的影响。
