Copolymerization of terephthalaldehyde with pyrrole, indole and carbazole gives microporous POFs functionalized with unpaired electrons

Abstract

A new family of paramagnetic microporous polymeric organic frameworks (POFs) has been developed through the co-polymerization of terephthalaldehyde and pyrrole, indole, and carbazole, respectively.These POFs are functionalized with stable unpaired electrons and electron paramagnetic resonance spectroscopy and pulsed ENDOR spectroscopy confirms their existence. The free radicals are produced in the early steps of polymerization and are responsible for their optical properties and the chemical adsorption properties of the POFs. The optical band gap of these materials ranges from 0.8 to 1.6 eV.The new POFs have spherical morphology and exhibit surface areas up to 777 m 2 g À1 (Pyr-POF-1).Furthermore, Pyr-POF-1 displays the uptake of CO 2 14% wt and C 2 H 6 9% wt at 273 K/1 bar and H 2 1.2% wt at 77 K/1 bar. The pyrrole based material (Pyr-POF-2) shows high capacity for CO 2 , 10% wt, under ambient conditions (298 K/1 bar) and the isosteric heat of CO 2 adsorption of $34 kJ mol À1 . The preparation of this new POF family is based on a very simple synthetic pathway and highlights the significance of terephthalaldehyde as a precursor for the synthesis of low cost functional porous polymers.

Prefunctionalized Porous Organic Polymers: Effective Supports of Surface Palladium Nanoparticles for the Enhancement of Catalytic Performances in Dehalogenation

“…[23][24][25] In addition, the modularn ature of the synthesis of POPs has allowed the incorporationo fv arious functionalities for as pecific purpose. [26,27] Relative to an extensive research in the functionality of POPs directed at gas sorptiona nd separation, [28][29][30] the pre-designable functionalities for immobilization of metal NPs have seldom been explored.…”

Triazine containing N-rich microporous organic polymers for CO 2 capture and unprecedented CO 2 /N 2 selectivity

“…However, major drawback of the MOF material is the difficulty in their synthesis in the large scale to meet the industry demand. Pure microporous carbon based materials such as covalent organic framework (COFs) [14], porous organic polymers [15], hypercrosslinked polymers (HCPs) [16], resins [17] N-doped microporous carbon [18], POFs [19] etc. have shown tremendous potential in the CO2 storage applications.…”

Microporous Organic Polymer‐Derived Nitrogen‐Doped Porous Carbon Spheres for Efficient Capacitive Energy Storage

“…The molecular linkages are also verified by 13 C CP‐MAS NMR spectroscopy (Figure S1b, ESI†). The peaks at 109, 120, 124 and 139 ppm are due to the overlapping of carbazole moieties connected at C‐3 and C‐6 atoms . The peak at 58 ppm can be attributed to the presence of methine linkages in the material.…”

“…The peaks at 109, 120, 124 and 139 ppm are due to the overlapping of carbazole moieties connected at C-3 and C-6 atoms. [43] The peak at 58 ppm can be attributed to the presence of methine linkages in the material. FE-SEM images of the CTS polymeric framework reveal nearly uniform spherical particles of~3-4 μm in diameters (Figure 1a).…”

“…1, 4‐dioxane was distilled over 4 Å molecular sieves. Carbazole‐terephthalaldehyde based co‐polymer spheres (CTS) were synthesized according to the procedure available in the literature …”