Microporous and Mesoporous Materials ( IF 5.2 ) Pub Date : 2020-10-27 , DOI: 10.1016/j.micromeso.2020.110728 Marco Fabbiani , Giorgia Confalonieri , Sara Morandi , Rossella Arletti , Simona Quartieri , Mario Santoro , Francesco Di Renzo , Julien Haines , Riccardo Fantini , Gloria Tabacchi , Ettore Fois , Giovanna Vezzalini , Gabriele Ricchiardi , Gianmario Martra
Zeolites are known as scaffolds for the assembly of molecules via non-covalent interactions yielding organized supramolecular materials. Yet their potential in driving the growth of low-dimensional systems requiring covalent bond formation is still unexplored. We incorporated 1,5-hexadiene in the channels of a high-silica mordenite and analyzed the material by infrared spectroscopy, X-ray powder diffraction, thermogravimetry and modeling techniques. Due to the few zeolite acid sites, 1,5-hexadiene experiences a slow conversion to a polymer mainly formed by cyclopentane units and featuring short side chains that are able to fit the channels. The shape-directing abilities of zeolite frameworks play a two-fold role, involving first the organization of the monomers inside the void-space and then the linear growth of the chain dictated by the channel geometry. These findings highlight the molding action of zeolites in directing transformations of covalent bonds under ambient conditions and may provide insights for obtaining confined polymers with intriguing prospective applications.
中文翻译:
通过模制纳米通道控制聚合物的生长:在高二氧化硅丝光沸石中进行1,5-己二烯聚合
沸石被称为支架,用于通过非共价相互作用产生有组织的超分子材料的分子组装。然而,它们在驱动要求共价键形成的低维体系增长方面的潜力仍未得到开发。我们在高硅丝光沸石的通道中加入了1,5-己二烯,并通过红外光谱,X射线粉末衍射,热重分析和建模技术对材料进行了分析。由于很少的沸石酸位,1,5-己二烯经历了缓慢转化为主要由环戊烷单元形成,并具有能够适合通道的短侧链的聚合物。沸石骨架的形状导向能力起着双重作用,首先涉及空隙空间内单体的组织,然后是由通道几何形状决定的链的线性增长。这些发现突出了沸石在环境条件下指导共价键转化的模制作用,并可能为获得具有吸引力的预期应用的受限聚合物提供见解。