Suenaga Kazumasa, Tanaka Kazuo, Chujo Yoshiki
Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto, 615-8510, Japan.
Chemistry. 2017 Jan 26;23(6):1409-1414. doi: 10.1002/chem.201604662. Epub 2016 Dec 19.
The development of a heat-resistant mechanoluminescent chromic (MLC) dye based on an organic-inorganic hybrid molecular scaffold is reported. Luminescent organoboron complexes were introduced into polyhedral oligomeric silsesquioxane (POSS) at each vertex through the rigid linker structure in the Suzuki-Miyaura cross-coupling reaction. From optical measurements, it was found that the crystalline state of the modified POSS showed orange emission. By adding mechanical forces to the sample, regular structures collapsed. Correspondingly, the emission color turned to yellow. Interestingly, the yellow-emissive amorphous state can be preserved during heating. By radially distributing luminescent chromophores on the rigid cube, both optical and thermal properties can be modulated to realize heat- resistant MLC behavior. POSS can contribute not only to expressing the MLC behavior, but also to improving thermal stability in the amorphous state. This is the first example, to the best of our knowledge, to offer the rational design of a heat-resistant MLC material.
报道了一种基于有机-无机杂化分子支架的耐热机械发光变色(MLC)染料的研制。通过铃木-宫浦交叉偶联反应中的刚性连接结构,将发光有机硼配合物引入到位于每个顶点的多面体低聚倍半硅氧烷(POSS)中。通过光学测量发现,改性POSS的晶态呈现橙色发射。对样品施加机械力后,规则结构坍塌。相应地,发射颜色变为黄色。有趣的是,黄色发射的非晶态在加热过程中可以保留。通过在刚性立方体上径向分布发光发色团,可以调节光学和热性能以实现耐热MLC行为。POSS不仅有助于表现出MLC行为,还有助于提高非晶态的热稳定性。据我们所知,这是首个提供耐热MLC材料合理设计的例子。