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62 Chapter 4<br />
partial replacing of BTC by the homologous pyridine-3,5-dicarboxylate (pydc) linker and<br />
revealed enhanced catalytic activity of the modified MOF in the oxidation of benzene<br />
derivatives related to modified M-CUS at the nodes. [136] Subsequently, studies conducted<br />
at our group demonstrated that not only pydc, but also a series of other defect generating<br />
linkers can be framework incorporated in case of [Cu3(BTC)2]n. [139] Interestingly,<br />
functionalized mesopores along with the M-CUS appeared to be generated in such defectengineered<br />
MOFs (DEMOFs) (Figure 4.4).<br />
Figure 4.4. The modulation of the defect structure on the micro- and mesoscales by doping of the<br />
framework with DL. The blue and short red sticks represent perfect and defective linkers. The<br />
yellow and black balls represent perfect and defective metal sites, respectively. The green<br />
highlighted unit indicates parent micropores. Reprinted with permission from Z. Fang, J. P.<br />
Dürholt, M. Kauer, W. Zhang, C. Lochenie, B. Jee, B. Albada, N. Metzler-Nolte, A. Pöppl, B. Weber, M.<br />
Muhler, Y. Wang, R. Schmid and R. A. Fischer, J. Am. Chem. Soc., 2014, 136, 9627-9636. Copyright<br />
(2014) American Chemical Society. [139]<br />
In parallel, Hupp et al. gave an account of the enhanced porosity by introducing<br />
isophthalate (ip) into [Cu3(BTC)2]n. [140] The concept of defect engineering by a mixed<br />
component approach using fragmented linkers together with the parent one was also<br />
expanded to the isostructural Ru-analogue. [138] Ru-DEMOFs [Ru3(BTC)2-x(pydc)xYy]n (Y =<br />
counter-ion, Cl - , OH - , OAc, etc.; 0 < y≤ 1.5) were obtained through direct mixing of H2pydc<br />
and H3BTC in one-step solvothermal synthesis. The generation of reduced Ru δ + (0
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