Design and Synthesis of Luminescent Liquid Crystalline Polymers with "Jacketing" Effect and Luminescent Patterning Applications
Design and Synthesis of Luminescent Liquid Crystalline Polymers with "Jacketing" Effect and Luminescent Patterning Applications
复制标题
具有“夹套”效应的发光液晶聚合物的设计与合成及发光图案化应用
DOI：
10.1021/acs.macromol.9b00221
复制
发表时间：
2019
期刊：
影响因子：
5.5
通讯作者：
Ben Zhong Tang
中科院分区：
文献类型：
--
作者：
Ji Chun Zhu;Ting Han;Yang Guo;Ping Wang;He-Lou Xie;Zhen Gong Meng;Zhen Qiang Yu;Ben Zhong Tang
为了制备发光液晶聚合物，设计并合成了两种单体2，5-bis[(4′，4″-dibutyloxy)tetraphenylphthalate]styrene(M1)和2，5-bis[(4′，4″-dibutyloxy)tetraphenylethylene]styrene(M2)。虽然M_1和M_2没有液晶性质，M_1在固体中不发射，但M_2具有很强的固体发射，荧光量子产率(Φ_F)为27.7%。理论计算结果表明，M2比M1更好的固态发光行为可以归因于光致电子转移效应的消除。M1和M2之间的结构差异也导致了聚合性的显著差异。虽然M1可以很容易地通过自由基聚合法进行均聚合，但M2只能在苛刻的条件下进行共聚。变温一维广角X射线衍射结果表明，均聚物poly{2，5-bis[2-(4，4′-dibutyloxy)tetraphenylphthalate]styrene}(P0)和共聚物poly{2，5-bis[(4′，4″-dibutyloxy)tetraphenylethylene]styrene}x–{[2，5-di(hexylformate)]styrene}y(Pns，n=1、2、3均为典型的柱状液晶相。与它们的相应单体类似，P0在固态时发射较弱，Φf值为2.0%，而P0在Φf值为18.0-45.1%范围内抑制了较强的固态荧光。共聚物的ΦF值随组成M2含量的增加而增大。得到的PnS具有良好的溶液可加工性，可以通过纳米压印光刻技术制备出高分辨率的高发光二维图形，这表明PnS在先进的光电子学和生物光子器件中具有潜在的应用前景。
To fabricate luminescent liquid crystalline polymers (LLCs), two monomers 2,5-bis[(4′,4″-dibutyloxy)tetraphenylphthalate]styrene (M1) and 2,5-bis[(4′,4″-dibutyloxy)tetraphenylethylene]styrene (M2) have been successfully designed and synthesized. AlthoughM1andM2show no LC property andM1is nonemissive in the solid state,M2shows very strong solid-state emission with a fluorescence quantum yield (ΦF) of 27.7%. The better solid-state luminescence behavior ofM2thanM1can be attributed to the elimination of the photoinduced electron transfer effect as suggested by the theoretical calculation results. The structural difference betweenM1andM2also results in a dramatical difference of polymerizability. WhileM1can be readily homopolymerized using the radical polymerization method,M2can only be copolymerized under harsh conditions. The resulting homopolymer poly{2,5-bis[2-(4,4′-dibutyloxy)tetraphenylphthalate]styrene} (P0) and copolymers poly{2,5-bis[(4′,4″-dibutyloxy)tetraphenylethylene] styrene}x–{[2,5-di(hexylformate)]styrene}y(Pns,n= 1, 2, 3) all show typical columnar liquid crystal phase (ColH) as demonstrated by the variable-temperature 1D wide-angle X-ray diffraction results. Similar to their corresponding monomers,P0is weakly emissive with a low ΦFof 2.0% in the solid state whereasPnsexhibit strong solid-state fluorescence with ΦFin the range 18.0–45.1%. The ΦFvalue of the copolymers increases with the increasing contents of compositionM2. The obtainedPnswith good solution processability can be used to prepare highly luminescent two-dimensional patterns with high resolution through nanoimprint lithography, which reveals thatPnsfind potential applications in advanced optoelectronic and biophotonic devices.