Coordination polymers construction

The network structures to be discussed will all involved hydrogen bonding as the supramolecular synthon. It should be noted however that other interactions such as coordinate bonds and host-guest interactions may also organise host molecules into network structures. Coordination polymers constructed from molecular hosts may involve functionalised calixarenes [8-11], cyclotriveratrylene [12], or cucurbituril [13]. Calixarenes have also been used to build up network structures via host-guest interactions [14,15]. It is also notable that volatile species may be trapped within the solid state lattice of calix[4] arene with a structure entirely composed of van der Waals interactions [16]. 

Figure 3.16 The structure of [Tb(bpdc)i 5(H2O)] 0.5nDMF. (a) The paddle-wheel building block, (b) The 3D-framework showing the large rhombic channels (Tb, black O, grey C, white H, omitted DMF guest molecules in (b) have been removed for clarity). (Redrawn from the CIF file of X. Guo et al., Synthesis, structure and luminescent properties of rare earth coordination polymers constructed from paddle-wheel building blocks, Inorganic Chemistry, 44 (11), 3850-3855, 2005 [75].)...

Guo, X., Zhu, G, Fang, Q., Xue, M., Tian, G, Sun, J. etal. (2005) Synthesis, stmcture and luminescentproperties of rare earth coordination polymers constructed from paddle-wheel building blocks. Inorganic Chemistry, 44(11), 3850-3855. 

Table 1. Uranyl coordination polymers constructed from oxalate linkages.

Table 7. Coordination polymers constructed from other actinide elements...

Tetra- and trinuclear SBUs have also been reported as constituents of porous and magnetic coordination polymers. Coordination polymers constructed around Co [144] and cubane-like Ln [145] assemblies have been reported, and these systems present contrasting porosity and robustness, but show only weak and predominant antiferromagnetic interactions at low temperature. Very recently, Yang and co-workers described a series of 3-D lanthanide-transition MOFs constructed around two distinct tetranuclear units of Ln cubanes and chair-like Cu clusters [146]. 

Completely different behaviours are observed in the coordination polymers constructed from azpy and bped ligands (Fig. 23), in which guest ethanol molecules... 

It is well known that porous zeolites show cation-exchange properties due to their anionic frameworks, while porous coordination polymers constructed from cationic metal ions and... 

The earliest examples of coordination polymers constructed through the node-and-spacer approach utilized metal ions as nodes and neutral N-donor ligands as spacers. Examples of neutral N-donor ligands utilized in the construction of coordination polymers include pyrazine, 4,4 -bipyridine, ° pyrimidine, triazine, and hexamethylenetetramine (HMTA) (Figures 4-6). Examples of permanently porous MOFs based on neutral N-donor ligands are scarce, mainly due to the relatively flexible nature of the N-M bonds around the metal center.In addition, framework interpenetration is commonly observed in this class of coordination polymers, limiting the maximal attainable pore size in isoreticular compounds constructed through expansion of the linker. ... 

Since chalcogen groups are also potential redox-active sites, we have studied the coordination polymers constructed by bridging ligands with chalcogen sites. For the syntheses of coordination polymers with sulfide and disulfoxide sites, 4-pyridylthioacetate (pyta), 4,4 -sulfonyldibenzoate... 

Sun Y-G, Yu W, Wang L et al (2010) Synthesis, structures, and luminesctaice of lanthanide coordination polymers constructed from benzimidazole-5,6-dicarboxylate and oxalate ligands. Inorg Chem Commun 13 479-483... 

Xia J, Zhang Z-J, Shi W et al (2010) Copper(I) cyanide coordination polymers constructed from bis(pyrazole-l-yl)alkane ligands observation of the odd-even dependence in the structures. Cryst Growth Des 10 2323-2330... 

Noro S-i, Kitagawa S, Akutagawa T, Nakamura T. Coordination polymers constructed from transition metal ions and organic N-containing heterocyclic ligands Crystal structures and microporous properties. Prog Polym Sci 2009 3 240-79. 

Zhu S, Zhang H, Zhao Y, Shao M, Wang Z, Li M. Synthesis, structures and luminescence of three coordination polymers constructed from rigid 1,3,5-benzenetricarboxylic acid and flexible bis(imidazol-l-yhnethyl)-benzene. J Mol Struct 2008 892 420-6. 

Zhao Y-H, Su Z-M, Fu Y-M, Shao K-Z, Li P, Wang Y, et al. Syntheses and characterizations of four metal coordination polymers constructed by the pyridine-3,5-dicarboxylate ligand. Polyhedron 2008 27 583-92. 

To date, only one example has been reported of a 2D cadmium coordination polymer constructed with thiocyanate and nicotinamide. In the referred polymer, each Cd " ion, located in a centrosymmetric octahedral environment, is coordinated by two nicotinamide molecules in traits positions and four thiocyanate ions, which act as N,S bridging ligands that link to four neighboring cadmium ions [70]. 

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