A HKUST-1 MOF inclusion compound with in-situ reduced copper(I) as [Cu(NCCH3)4]+ cation complex in the octahedral A-type pore

Hydrothermal reaction of racemic 1,2-bis(1,2,4-triazol-4-yl)propane (rac-btrip) and benzene-1,3,5-tricarboxylic acid (H3btc) with copper(II) acetate in an aqueous triethylamine and acetonitrile mixture afforded blue-green cuboctahedral crystals of the MOF inclusion compound 3D-{[Cu(NCCH3)4][Cu3(μ6-btc)2]2(O2CCH3) (H2O,CH3CN)x(btrip)1.5}n, 1. This MOF is isostructural with the prototypical MOF HKUST-1 (Cu3(btc)2, Cu-btc) and the first HKUST-1 derivative which accommodates a defined guest, namely the cationic tetra(acetonitrile)copper(I) complex [Cu(NCCH3)4]+ in the A-type octahedral pores of the 3D HKUST-1 framework. In-situ reduction of Cu(II) to Cu(I) in the course of the hydrothermal synthesis is afforded by the sacrificial btrip ligand which is not incorporated as a linker but as a template molecule into the cuboctahedral B- and C-type pores according to 1H NMR digestion analysis. N2 adsorption isotherm analysis for the activated HKUST-1 inclusion compound 1 gave a BET surface area of 576 m2/g.

Graphical abstractThe first HKUST-1 inclusion derivative with a defined guest in the octahedral A-type pores.Figure optionsDownload full-size imageDownload as PowerPoint slide