Regioselective Functionalization of the Mesoporous Metal-Organic Framework, NU-1000, with Photo-Active Tris-(2,2'-bipyridine)ruthenium(II)

介孔金属有机骨架 NU-1000 与光活性三-(2,2'-联吡啶)钌 (II) 的区域选择性功能化

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作者:Hisanori Nagatomi, Leighanne C Gallington, Subhadip Goswami, Jiaxin Duan, Karena W Chapman, Nobuhiro Yanai, Nobuo Kimizuka, Omar K Farha, Joseph T Hupp

Abstract

Solvent-assisted ligand incorporation is an excellent method for the post-synthetic functionalization of Zr-based metal-organic frameworks (MOFs), as carboxylate-derivative functionalities readily coordinate to the Zr6 nodes by displacing node-based aqua and terminal hydroxo ligands. In this study, a photocatalytically active ruthenium complex RuII(bpy)2(dcbpy), that is, bis-(2,2'-bipyridine)-(4,4'-dicarboxy-2,2'-bipyridine)ruthenium, was installed in the mono-protonated (carboxylic acid) form within NU-1000 via SALI. Crystallographic information regarding the siting of the ruthenium complex within the MOF pores is obtained by difference envelope density analysis. The ruthenium-functionalized MOF, termed Ru-NU-1000, shows excellent heterogeneous photocatalytic activity for an oxidative amine coupling reaction.

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