Mixed precious-group metal-organic frameworks: a case study of the HKUST-1 analogue [RuxRh3-x(BTC)2]

This work presents the first full series of mixed precious-group metal-organic frameworks (MPG-M0Fs) using ruthenium and rhodium. The obtained crystalline, highly porous and thermally robust materials were characterized by means of powder X-ray diffraction, Nz/CO, sorption isotherms, thermogravimetry, spectroscopy methods (IR, Raman, UV/VIS-, NMR and XPS) and as well by high resolution transmission electron microscopy (HR-TEM) with elemental mapping (HAADF-EDS). Additionally, the assignment of spectroscopic data is supported by computational (time dependent)-density functional theory methods. The materials turned out to consist of homogeneously dispersed Ru, and Rhz paddlewheel units being linked by benzenetricarboxylate (BTC) to yield a framework that is isoreticular to [Cu3(BTC)21 (HKUST-1, Hong Kong University of Science and Technology). However, acetate (OAc) is incorporated as an intrinsic component which compensates for missing BTC-linker defects and some CI is coordinated to the Ru centre at an apical position. The exact empirical formula of the MPG-MOFs is derived as [RuxRh3-x(BTC)(2-a),(OAc)(b)(Cl)(c)].