Rhodium–Organic Cuboctahedra as Porous Solids with Strong Binding Sites

The upbuilding of dirhodium tetracarboxylate paddlewheels into porous architectures is still challenging because of the inertness of equatorial carboxylates for ligand-exchange reaction. Here we demonstrate the synthesis of a new family of metal–organic cuboctahedra by connecting dirhodium units through 1,3-benzenedicarboxylate and assembling cuboctahedra as porous solids. Carbon monoxide and nitric oxide were strongly trapped in the internal cavity thanks to the strong affinity of unsaturated axial coordination sites of dirhodium centers.

将二铑四羧酸盐桨轮型配合物（dirhodium tetracarboxylate paddlewheels）构筑为多孔架构仍颇具挑战，究其原因在于其赤道位点的羧酸盐配体对配体交换反应呈现惰性。本研究通过1,3-苯二甲酸盐（1,3-benzenedicarboxylate）连接二铑单元，将所得金属有机立方八面体组装为多孔固体，成功合成了一类全新的金属有机立方八面体家族。得益于二铑中心不饱和轴向配位位点的强亲和作用，一氧化碳与一氧化氮可被高效捕获于该材料的内部空腔中。