2D coordination polymer networks

The angular ligand 4,4 -dipyridylsulfide (dps) shown in Scheme 3 has been reacted with a variety of metal salts such as Zn(CH3COO)2, AgC104 and Cul in a 1 1 ratio to afford luminescent coordination polymers of these d10 ions.125 In the latter case, the resulting 2D polymer of composition [ Cu(g-I)2Cu (dps)2] 5 possessing a noninterpenetrating (4,4) network has been structurally analyzed. 

Several metal-organic polymers assembled by dithioether ligands, which are functionalized by heteroelements such as O, N, or Si in the spacer unit, have been recently described and reacted with Cu(I) salts. For example, the 2D square-grid coordination polymer 37 incorporating the 16-membered dithiaoxa crown-ether L37 has been prepared by a self-assembly process involving the interaction of the dithiaoxa macrocycle with CuCN (Scheme 17) the parallel reaction of the dithiaoxa crown-ether with Cul afforded the ID double-stranded coordination polymer 37 . This example demonstrates, how the nature of the counterion can control the form of the network.157... 

Kim s group also prepared the l,12-diphenyl-5,8-dioxa-2,ll-dithidodecane ligand L44 and reacted it with Cul.164 Contrary to our failure to assemble a network with 1,8 bis(phenylthio)octane, L44 containing eight spacer units between the sulfur atoms allowed the construction of a 2D square-grid-type coordination polymer 44. This finding may be rationalized by the enhanced basicity of -S-benzyl vs. -S-phenyl (Scheme 23). 

With 2,2 -bipyridine-3,3 -dicarboxylate (bpdc), also under hydrothermal conditions, a lanthanide coordination polymer [ Er4(/t3-OH)4(bpdc)4 (H20)6 2](H20)i6 is obtained wherein cubane-like [Er4(/t3-OH)4] " building blocks are assembled into a 2D network structure through the linkage of bpdc (Hu et al., 2007 Figure 101). 

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