Porous coordination polymers polymerizations

TMA can coordinate to not only Cu2+ to form the typical 3-D framework polymer but also to Co2+ to form a porous host-guest compound Co(TMA) (py) with a different structure. The guest pyridine molecules in this compound may be removed from the channels without the collapse of the framework, and the pyridine-removed porous material adsorbs other guest molecules.[187] Polymerization of TMA with a Ni2+ macro-cyclic complex leads to a porous coordination polymer with a unique structure. In the... 

Abstract Porous coordination polymers prepared via the self-assembly of metal ions and organic ligands have attracted considerable attention because of their potential applications in storage, separation, and catalytic systems. The use of their regulated nanochannels as the fields for polymerization can allow for precise control over the polymer structures. In addition, the confinement of polymer chains in the nanochannels allows for the formation of unique nanocomposites that show unprecedented and interesting dynamic, optical, and electronic properties. 

Uemura T, Kitaura R, Ohta Y, Nagaoka M, Kitagawa S. Nanochannel-promoted polymerization of substituted acetylenes in porous coordination polymers. Angew Chem, Int Ed 2006 45 4112-6. 

Wu CD, Lin W. Topotactic linear radical polymerization of divinylbenzenes in porous coordination polymers. Angew Chem Int Ed 2007 46 1075-8. 

LAG is particularly interesting for mechanochemical synthesis of porous frameworks and inclusion compounds, as the liquid can sometimes become incorporated into the final product as a guest and so direct (template) its structure. One example of mechanochemical formation of a metal-organic host-guest complex is the kneading of copper(II) chloride and dace in the presence of A,A-dimethylsulfoxide (DMSO) or water, which leads to the simultaneous in situ formation of the 1-D coordination polymer host [Cu(dace)Cl2] and molecular inclusion to form inclusion compounds such as [Cu(dace)Cl2] DMSO (Figure 2b). Importantly, the polymeric host itself is not obtainable by neat grinding... 

When the active centre is surrounded by a layer of solid polymer, further propagation will be controlled by the rate of monomer diffusion through the polymer layer. Usually it will be retarded. With a porous polymer layer surrounding the active centres, monomer transport will be easier. These effects must be considered when highly crystalline polymers are formed, especially when the chains grow from a non-transferring monomer as, for example, with coordination polymerizations [56],... 

By adsorbing the perylene derivative tetraazaperopy-rene (TAPP) on Cu(lll) and annealing at 150°C, a Cu-coordinated porous network develops. Annealing at even higher temperatures (250 °C) results in the formation of ID chains—most probably with the Cu substrate acting as a catalyst—which consist of covalently coupled TAPP monomers (Figure 10). The reaction is supposed to proceed via a carbene intermediate. The first example shows that a reaction, which is well known from solution chemistry, can be adopted for the construction of polymeric struc-tnres on surfaces. In contrast, the second example demonstrates that on-surface reactions can allow for the formation of polymers which cannot be obtained via solution-based chemistry at all. 

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