Dative PSM

Dative PSM this involves coordination of a metal center to a linker. 

Figure 1 Schematic representation of the three categories of PSM covered in this review, showing (a) covalent PSM, (b) dative PSM, and (c) two types of inorganic PSM...

For covalent or dative PSM, the MOF normally needs to have a reactive group present on a linker. This group is referred to as a tag, and this is defined as a group or functionality that is stable and innocent during MOF formation, but that can be transformed by a PSM. Sometimes, sequential PSM reactions are carried out. These are referred to as tandem reactions, and they typically involve either two or more consecutive covalent modifications or a covalent modification followed by a dative modification. 

Dative PSM involves the postsynthetic coordination of a metal center to one of the linker ligands. Examples of dative PSM reactions are summarized in Table 2. 

Another common approach to dative PSM uses a covalent reaction to assemble a ligand and then reacts this with a metal center in the second half of a tandem process. For example, Yaghi et al. showed how an iminopyridine-functionalized UMCM-1 derivative, obtained by covalent PSM, reacts with [PdCl2(MeCN)2] to give metallation of the bidentate coordination sites (equation 19). ... 

PSM now routinely allows for the synthesis of MOFs that cannot be made by other routes, either because the functional groups are not tolerant of the synthetic conditions (covalent and dative PSM) or because direct synthesis leads to other phases (covalent and inorganic PSM). Furthermore, modified materials have been demonstrated to possess enhanced gas adsorption capacities and selectivities, and higher catalytic activity than their unmodified counterparts. 

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