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

The coordination polymer {[Ni(C 20 H 32 N 8 )] 2 [TCM]} · 5DMF · 8H 2 O ( 1 ) has been assembled from a Ni II macrocyclic complex that contains two pyridyl pendant arms, [Ni(C 20 H 32 N 8 )](ClO 4 ) 2 , and sodium tetrakis[4‐(carboxyphenyl)oxamethyl]methane (Na 4 TCM) 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 Ni II macrocyclic species, and reacts with Pd(NO 3 ) 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.