Organic Polymers of an Angular Diene via Solid State [2 + 2] Polymerization: Coordination Polymers with Dicarboxylates as Templates

A new class of organic polymers have been synthesized via solid-state [2 + 2] photopolymerization reaction of coordination polymers (CPs) of an angular diene, namely, 3,3′-(1,3-phenylene)bis(N-(3-pyridyl)acrylamide) (L), with dicarboxylates as ancillary ligands. Five CPs of L have been studied, which includes three types of dicarboxylates and five metal ions such as Co(II), Cu(II), Cd(II), Ni(II), and Zn(II). Two of the three dicarboxylates contain angular (isophthalate/glutarate) geometry and one contains linear geometry (terephthalate). The CPs with angular dicarboxylates exhibit 2D-layers containing M2L2 macrocycles, whereas the CPs with terephthalate exhibits 2D-corrugated layers containing rectangular grids. Four out of the five CPs are found to be photoreactive to produce coordination polymers of organic polymers (CPOPs) upon irradiation. The yields of solid state [2 + 2] polymerization reactions were calculated using 1H NMR spectra and the degree of polymerization have been determined by MALDI-TOF ...