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

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

doi:10.1021/acsomega.0c04823

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

ACS Omega. 2020 Nov 9;5(46):30299-30305. doi: 10.1021/acsomega.0c04823. eCollection 2020 Nov 24.

Authors

Affiliations

¹ Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
² Department of Chemistry and Biochemistry, Graduate School of Engineering, Center for Molecular Systems (CMS), Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.
³ X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439-4858, United States.
⁴ Department of Chemistry, Stony Brook University, 100 Nichols Rd, Stony Brook, New York 11794-3400, United States.
⁵ JST-PRESTO, Honcho 4-1-8, Kawaguchi, Saitama 332-0012, Japan.

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 Ru^II(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.