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Chapter 2 19<br />
the rection of H2dacobdc, bipyridine and Zn(II) in DMF, with the simultaneous removal of<br />
the acetoxyl groups completely. This strategy was found to be useful for preventing<br />
interpenetration, introducing functionality, and controlling pore diameter. [105]<br />
Figure 2.12. A general scheme illustrating the concept of post-synthetic modification (PSM) on<br />
organic likers or metal-containing nodes of MOFs. Top, covalent PSM; Middle, dative PSM; Bottom,<br />
PSD. Reprinted with permission from S. M. Cohen, Chem. Rev., 2012, 112, 970-1000. [101] . Copyright<br />
(2012) American Chemical Society.<br />
Moreover, dative PSM (Figure 2.12 middle) involves heterogeneous chemical reactions to<br />
functionalize preassembled MOF structures via modification of metal-containing nodes<br />
(SBUs) [106-107] or organic linkers [108] can be reached via the formation of dative (i.e. metalligand)<br />
bond. [101] One of the first representative studies on dative PSM was reported by<br />
Hupp et al. [106] It was found that axially bound DMF solvent molecules in the PW SBUs<br />
could be fully removed from the Zn(II) PW-derived MOF by heating under vacuum.<br />
Subsequently the desolvated MOF was treated with pyridine derivatives in CH2Cl2, leading<br />
to materials in which the axial sites left vacant on the SBUs can be bound with pyridine<br />
derivatives. Those obtained MOF materials demonstrated dependent H2 uptake on the<br />
pyridine species coordinated to the SBUs, indicating properties could be<br />
modulated/optimized by dative PSM. Férey and co-workers reported amine grafting on
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