Synthesis and characterization of 2-D and 3-D covalent networks derived from triazine central cores and bridging aromatic diamines

Nucleophilic substitutions of the reactive chlorine atoms in either cyanuric or phosphonitrilic chloride by the bridging 1,4-phenylenediamine and benzidine units lead to the formation of two- (2-D) or three-dimensional (3-D) covalent networks, according to the spatial arrangement of the chlorine atoms in each particular triazine core. The materials are electrochemically active and stable, and exhibit interesting optical properties. The UV–visible spectral absorptions are significantly red-shifted and can been altered upon chemical oxidation. Furthermore, a three-band absorption spectrum typical of polaronic nature is observed in the case of the layered benzidine/cyanuric chloride network. Either spherical (2-D) or cubic (3-D) morphologies were revealed by SEM analysis, while the XRD patterns indicated partial crystallinity. Due to the inherited ion-exchange properties of the 2-D and 3-D ionic networks, the materials can be regarded as the organic analogues of conventional inorganic layered or zeolitic ion-exchangers.