Toward Tailorable Porous Organic Polymer Networks: A High-Temperature Dynamic Polymerization Scheme Based on Aromatic Nitriles

Abstract

Triazine-based polymer scaffolds with controllable porosity were prepared through a dynamic polymerization scheme based on a broad variety of aromatic nitriles, upon polytrimerization of the latter from ZnCl 2 salt melts at high temperatures. In the present study, the reaction parameters such as the temperature and monomer concentration as well as the geometry and functionality of the monomers were systematically varied. A comprehensive overview of the influences of these parameters on the outcome of the polymerization reaction in terms of chemical nature and porous properties of the materials is proposed. Rather than the variation of the monomer size and/or geometry, the reaction parameters were found to play a crucial role for tuning the porosity of the materials and especially the reaction temperature. Finally, the use of functional aromatic bridging units allowed the formation of functional polymer scaffolds with the ability to coordinate metal salts, introducing the possibility to design new metallo-organic materials.

Aromatic porous-honeycomb electrodes for a sodium-organic energy storage device

“…Its poresize distribution confirmed the existence of micropores of ca.1.4 nm (Fig. 1a), which was observed by previous reports [29][30][31] ( Fig. 2b).…”

“…S2) gives a further details about the BPOE: This framework is formed as a short-range-ordered 2D structure with the stacking of each 2D unit (Fig. 1a) in a noncoplanar fashion [29][30][31] as the global structure. Raman spectroscopy measurements (RSMs) allow to reveal the electronic structure of materials ( ¼ information about a structural periodicity of a material) [32][33][34] .…”

A functional triazine framework based on N-heterocyclic building blocks

“…Owing to the abundance of metal bipy complexes known and the versatility of the bipy ligand in homogeneous catalysis, a CTF framework based on this ubiquitous type of ligand may ultimately provide a link between a homogeneous catalyst and its heterogeneous counterpart, both featuring a metal bipy unit as the catalytically active site. First attempts to synthesize a bipy CTF have been made by Kuhn et al recently, 14 yet the resulting amorphous powders were reported to possess no apparent porosity and a surface area of essentially zero. In the present paper we demonstrate the synthesis of a highly porous bipy CTF and give a detailed account of the complex interplay between local and long range order, porosity, and nitrogen content to enable a deeper under standing of the structure and a more rational approach to the design of covalent triazine frameworks.…”

Carbonization of covalent triazine-based frameworks via ionic liquid induction

“…This behavior is attributed to the consumption of the monomer during the reactions. The peaks at 1523 and 1351 cm -1 in KPOP-6a and KPOP-6b's spectra confirm the formation of triazine rings 11,[35][36][37] while the very weak intensity of the corresponding peaks in the spectra of KPOP-6c, KPOP-6d, and KPOP-6e is indicative of the triazine decomposition. …”