Moreno José María, Velty Alexandra, Díaz Urbano, Corma Avelino
Instituto de Tecnología Química , Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas , Avenida de los Naranjos s/n , E-46022 Valencia , Spain . Email:
Chem Sci. 2018 Dec 17;10(7):2053-2066. doi: 10.1039/c8sc04372h. eCollection 2019 Feb 21.
Novel MOF-type materials with different morphologies based on assembled 1D organic-inorganic sub-domains were prepared using specific monodentate benzylcarboxylate spacers with functional substituents in the para-position as structure modulating agents. The combination of electron-withdrawing or electron-donating functions in the organic spacers with suitable solvothermal synthesis conditions allowed modulating the structuration level (2D or 3D), vacancies, physico-chemical properties and Lewis acidity strength of the metal-organic structures. Furthermore, bimetallic (Al/Fe) MOF-type materials were synthesized by a one-pot direct process without modification of the structural framework. The activity of these hybrid materials as Lewis acid catalysts was evaluated to prepare cyanohydrins as precursors for the synthesis of biologically active compounds, and for aerobic oxidation of thiols to disulfides. The catalytic results showed that the derived MOFs exhibited modulatable Lewis acid capacities which are a function of the morphology, functionality of monodentate substituents present in the networks and a cooperative effect between metallic nodes of different nature.
基于组装的一维有机-无机子域，使用对位置带有官能取代基的特定单齿苄基羧酸盐间隔物作为结构调节剂，制备了具有不同形态的新型金属有机框架（MOF）型材料。有机间隔物中吸电子或供电子功能与合适的溶剂热合成条件相结合，能够调节金属有机结构的结构化水平（二维或三维）、空位、物理化学性质和路易斯酸强度。此外，通过一锅直接法合成了双金属（铝/铁）MOF型材料，而无需对结构框架进行改性。评估了这些杂化材料作为路易斯酸催化剂的活性，用于制备氰醇作为合成生物活性化合物的前体，以及用于将硫醇有氧氧化为二硫化物。催化结果表明，衍生的金属有机框架表现出可调节的路易斯酸容量，这是形态、网络中存在的单齿取代基的官能度以及不同性质的金属节点之间协同效应的函数。
