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Flexible and Redox-Active Coordination Polymer: Control of the Network Structure by Pendant Arms of a Macrocyclic Complex



The coordination polymer {[Ni(C20H32N8)]2[TCM]}·5DMF·8H2O (1) has been assembled from a NiII macrocyclic complex that contains two pyridyl pendant arms, [Ni(C20H32N8)](ClO4)2, and sodium tetrakis[4-(carboxyphenyl)oxamethyl]methane (Na4TCM) in DMF/water. The X-ray structure of 1 reveals that the pyridyl pendant arms in the macrocyclic complex play a crucial role in determining the network structure through the π–π interactions. Compound 1 forms doubly catenated rhombic grids that generate 1D channels. It exhibits flexible behavior upon desorption/resorption and exchange of organic guest molecules as well as temperature change. Solid 1 is redox active due to the incorporated NiII macrocyclic species, and reacts with Pd(NO3)2 dissolved in acetonitrile at room temperature to produce small Pd nanoparticles [(2.9 ± 0.4) nm in diameter] in the channels in the absence of extra reducing or capping agents.