Lambov Martin, Hensiek Nicola, Pöppler Ann-Christin, Lehmann Matthias
Institute of Organic Chemistry, University of Würzburg, Am Hubland, 97074, Würzburg, Germany.
Center for Nanosystems Chemistry and Bavarian Polymer Institute, Theodor-Boveri-Weg 4, 97074, Würzburg, Germany.
Chempluschem. 2020 Oct;85(10):2219-2229. doi: 10.1002/cplu.202000341. Epub 2020 Jul 21.
Shape-persistent conjugated mesogens with oligothiophene arms of different lengths have been synthesized. Such mesogens possess free intrinsic space between their conjugated arms. They form columnar liquid-crystalline phases, in which the void is filled by dense helical packing in the neat phase similar to an oligo(phenylene vinylene) derivative of equal size. The void can also be compensated by the inclusion of the small acceptor molecule 2,4,7-trinitrofluorenone. In solution, the acceptor interacts with the core as the largest π-surface, while in the solid material, it is incorporated between the arms and sandwiched by the star-shaped neighbours along the columnar assemblies. The TNF acceptors are not nanosegregated from the star-shaped donors, thus the liquid crystal structure converts to a nano-reservoir for TNF (endo-receptor). These host-guest arrangements are confirmed by comprehensive X-ray scattering experiments and solid-state NMR spectroscopy. This results in ordered columnar hexagonal phases at high temperatures, which change to helical columnar mesophases or to columnar soft crystals at room temperature.
已合成出具有不同长度低聚噻吩臂的形状持久共轭介晶。这类介晶在其共轭臂之间具有自由的固有空间。它们形成柱状液晶相，在纯相中，空隙通过致密的螺旋堆积填充，这类似于相同尺寸的聚对苯撑乙烯衍生物。空隙也可以通过包含小的受体分子2,4,7-三硝基芴酮来补偿。在溶液中，受体与作为最大π表面的核心相互作用，而在固体材料中，它被纳入臂之间，并沿着柱状聚集体被星形邻居夹在中间。TNF受体与星形供体没有纳米分离，因此液晶结构转变为TNF的纳米储存器（内受体）。这些主客体排列通过综合X射线散射实验和固态核磁共振光谱得到证实。这导致在高温下形成有序的柱状六方相，在室温下转变为螺旋柱状中间相或柱状软晶体。
