Inhibition, Binding of Organometallics, and Thermally Induced CO Release in an MFU-4-Type Metal-Organic Framework Scaffold with Open Bidentate Bibenzimidazole Coordination Sites

Richard Röß-Ohlenroth; Maryana Kraft; Hana Bunzen; Dirk Volkmer

doi:10.1021/acs.inorgchem.2c02394

Inhibition, Binding of Organometallics, and Thermally Induced CO Release in an MFU-4-Type Metal-Organic Framework Scaffold with Open Bidentate Bibenzimidazole Coordination Sites

Inorg Chem. 2022 Oct 17;61(41):16380-16389. doi: 10.1021/acs.inorgchem.2c02394. Epub 2022 Oct 5.

Authors

Richard Röß-Ohlenroth¹, Maryana Kraft¹, Hana Bunzen¹, Dirk Volkmer¹

Affiliation

¹ Chair of Solid State and Materials Chemistry, Institute of Physics, University of Augsburg, Universitätsstr. 1, D-86159 Augsburg, Germany.

PMID: 36197843
DOI: 10.1021/acs.inorgchem.2c02394

Abstract

Triazolate-based MFU-4-type metal-organic frameworks are promising candidates for various applications, of which heterogeneous catalysis has emerged as a hot topic owing to the facile post-synthetic metal and ligand exchange in Kuratowski secondary building units (SBUs). Herein, we present the largest non-interpenetrated isoreticular MFU-4-type framework CFA-19 ([Co₅^IICl₄(H₂-bibt)₃]; H₄-bibt = 1,1',5,5'-tetrahydro-6,6'-biimidazo[4,5-f]benzotriazole; CFA-19 = Coordination Framework Augsburg University-19) and the CFA-19-Tp derivative featuring trispyrazolylborate inhibited SBUs as a scaffold with open bibenzimidazole coordination sites at the backbone of the H₄-bibt linker. The proof-of-principle incorporation of accessible M^IBr(CO)₃ (M = Re, Mn) sites in CFA-19-Tp was revealed by single-crystal X-ray diffraction, and a thermally induced CO release was observed for MnBr(CO)₃. Deprotonation of bibenzimidazole was also achieved by the reaction with ZnEt₂.