Regioselective Functionalization of the Mesoporous Metal–Organic Framework, NU-1000, with Photo-Active Tris-(2,2′-bipyridine)ruthenium(II)
journal contributionposted on 10.11.2020, 03:43 by Hisanori Nagatomi, Leighanne C. Gallington, Subhadip Goswami, Jiaxin Duan, Karena W. Chapman, Nobuhiro Yanai, Nobuo Kimizuka, Omar K. Farha, Joseph T. Hupp
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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Crystallographic informationterminal hydroxo ligandsdifference envelope density analysisRu IIcarboxylate-derivative functionalitiespost-synthetic functionalizationdisplacing node-based aquaSALIoxidative amineZr 6 nodesRegioselective Functionalizationcarboxylic acidruthenium-functionalized MOFNU -1000photocatalytic activityMOF pores