Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany.
Dalton Trans. 2018 Oct 16;47(40):14340-14351. doi: 10.1039/c8dt03254h.
Crown ethers and their derivatives are versatile building blocks for the design of supramolecular materials. They can be functionalized at will and are well known for their abilities to complex with alkali cations. Here, we show that emissive lanthanide free hybrid materials can be generated by using such building blocks. The organic tribenzo[18]crown-6 central core was functionalized via six-fold Suzuki cross-coupling as a key reaction with three o-terphenyl units which could be converted into their corresponding triphenylenes by the Scholl reaction, leading to novel liquid-crystalline columnar materials. Selected tribenzo[18]crown-6 o-terphenyls could interact with emissive ternary metal cluster compound salts to generate hybrid materials combining the properties of both moieties. Due to synergistic effects and despite the anisometry of the cluster compounds, individual properties such as liquid-crystalline phase stability of the organic part and emission abilities of its inorganic counter-part are enhanced in the hybrid compounds.
冠醚及其衍生物是设计超分子材料的多功能构建块。它们可以随意功能化,并且以与碱金属阳离子络合的能力而闻名。在这里,我们展示了可以使用此类构建块生成发光的镧系元素自由杂化材料。通过六重铃木交叉偶联作为关键反应,用三个邻三联苯单元对有机三苯并[18]冠-6 中心核进行功能化,邻三联苯单元可以通过 Scholl 反应转化为相应的三联苯,从而得到新型液晶柱状材料。选择的三苯并[18]冠-6 邻三联苯可以与发光三元金属簇化合物盐相互作用,生成结合两个部分性质的杂化材料。由于协同效应,尽管簇化合物的各向异性,但其有机部分的液晶相稳定性和其无机对应物的发光能力等单个性质在杂化化合物中得到增强。