Abstract:
Porous liquids (PLs), a summation of porous hosts and bulky solvents bestowing permanent cavities, are the prominent emerging materials. Despite great efforts, exploration of porous hosts and bulky solvents is still needed to develop new PL systems. Metal-organic polyhedra (MOPs) with discrete molecular architectures can be considered as porous hosts; however, many of them are insoluble entities. Here we report the transformation of type III PL to type II PLs by tuning the surface rigidity of insoluble MOP, Rh24 L24 , in a bulky ionic liquid (IL). Functionalization of N-donor molecules on Rh-Rh axial sites ensue their solubilization in bulky IL which confer type II PLs. Experimental and theoretical studies reveal the bulkiness of IL as per the cage apertures, and the cause of their dissolution as well. The obtained PLs, capturing more CO2 than neat solvent, have depicted higher catalytic activity for CO2 cycloaddition compared to individual MOPs and IL.
摘要:
多孔液体(PL),多孔主体和大体积溶剂的总和赋予永久性空腔,是突出的新兴材料。尽管付出了巨大的努力,仍需要探索多孔主体和庞大的溶剂来开发新的PL系统。具有离散分子结构的金属有机多面体(MOP)可以被视为多孔主体;但是,其中许多是不可溶的实体。在这里,我们报告了通过调整不溶性MOP的表面刚度将III型PL转换为II型PL,Rh24L24,在年夜体积离子液体(IL)中。N-供体分子在Rh-Rh轴向位点上的官能化导致它们在大体积IL中的溶解,这赋予II型PL。实验和理论研究表明,按照笼孔,IL的体积较大,以及它们解散的原因。获得的PLs,捕获比纯溶剂更多的CO2,与单独的MOP和IL相比,已经描述了更高的CO2环加成催化活性。