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28 Chapter 3
3.1 Preparation and investigation of the Ru II,III -analogs of [M3(BTC)2]n *
3.1.1 The family of [M3(BTC)2]n
Figure 3.1. 3D crystal structure of [Cu 3 (BTC) 2 ] n (Cu-HKUST-1) viewed along the (100) direction.
Green, red and gray balls stand for Cu, O and C atoms, respectively. Hydrogen atoms are omitted
for clarity.
[Cu3(BTC)2]n (also known as HKUST-1 [35] or MOF-199 [36] , BTC = 1,3,5-
benzenetricarboxylate), first reported by Chui et al. in 1999, represents one of the most
well investigated MOFs synthesized at the early stages of MOF chemistry. The 3D
structure of [Cu3(BTC)2]n, with the space group Fm-3m, features paddlewheel (PW)
dicopper(II) tetracarboxylate building blocks where Cu II -ions adopt pseudo-octahedral
coordination geometry with the axial sites occupied by H2O (Figure 3.1). These
coordinated water molecules H2O can be easily removed by heating the samples under
vacuum (i.e., activation) leading to exposed Cu II -ions, which subsequently could serve as
active Lewis acid sites in catalytic reactions (Figure 3.2). [189-190] Moreover, the interaction
* The main results of this part are covered in the following publication: W. Zhang, O. Kozachuk, R. A. Fischer,
et al. Eur. J. Inorg. Chem. 2015, 3913–3920.