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124 Chapter 5
preferred like Cu 2+ . [261-263],[264] Still, due to kinetic reasons, these metal ions are difficult to
be crystallized within 3D structures [263-264] and, therefore, almost neglected in MOF
field. [265] Reports on MOFs featuring Pd-Pd, Pd-M PW nodes could not be even found.
Figure 5.2. (a) Structural and (b) schematic representations of the synthesis of the cuboctahedral
bimetallic MOPs. Reproduced from J. M. Teo, C. J. Coghlan, J. D. Evans, E. Tsivion, M. Head-Gordon,
C. J. Sumby and C. J. Doonan, Chem. Commun., 2016, 52, 276-279, with permission of The Royal
Society of Chemistry. [264]
Recent years the study of Ru-based MOFs has been mainly focused on the synthesis of Ruanalogues
of HKUST-1, which were successfully obtained in our group. [82, 198] Following
the previous studies, in this work the attention was turned also to palladium, which is well
known to facilitate dissociation of molecular hydrogen (spill-over effect). [266-268]
Furthermore, bimetallic Pd/M-paddlewheel (PW) complexes have been lately found to be
promising economical catalysts in the intramolecular benzylic C-H amination. [269]
Interestingly, to date immobilization of Pd-nanoparticles [270-273] and decoration of MOFs
interior with Pd-complexes [274-275] have been investigated a lot. Moreover, porous Pd 2+ -
M 2+ (M = Cu, Ni, Zn) metal-organic polyhedra have been very recently described (Figure
5.2). [264] Regardless obvious interest, studies on integration of palladium as a framework
node into a MOF are, however, in its infancy. [265, 276-277] Hence, considering its structural
peculiarities (i.e., PW SBUs and CUSs) [35] and primary experimentally studies on [Cu3-
xRux(BTC)2]n including Ru 3+ (rion = 68 pm), [257] it would be of interest to choose
[Cu3(BTC)2]n (Cu-BTC) as a matrix for in-framework incorporation of Pd 2+ (rion = 86