Porous organic polymers have been received considerable attention due to their heteroatom-containing structures and high surface areas, which can offer high electrochemical performance in energy applications. The majority of reported Tröger's base-functionalized porous organic polymers have been applied as effective candidates for sensing and gas separation/adsorption, while their use as electrode materials in supercapacitors is rare. Here, a novel covalent microporous organic polymer containing carbazole and Tröger's base CzT-CMOP has been successfully synthesized through the one-pot polycondensation of 9-(4-aminophenyl)-carbazole-3,6-diamine (Cz-3NH2) with dimethoxymethane. The polycondensation reaction's regioselectivity was studied using spectroscopic analyses and electronic structure calculations that confirmed the polycondensation occurred through the second and seventh positions of the carbazole unit rather than the fourth and fifth positions confirmed by first-principles calculations. Our CzT-CMOP exhibited high thermal stability of approximately 463.5 °C and a relatively high Brunauer-Emmett-Teller surface area of 615 m2 g-1 with a nonlocal density functional theory's pore size and volume of 0.48 cm3 g-1 and 1.66 nm, respectively. In addition, the synthesized CzT-CMOP displayed redox activity due to the existence of a redox-active carbazole in the polymer skeleton. CzT-CMOP revealed high electrochemical performance when used as active-electrode material in a three-electrode supercapacitor with an aqueous electrolyte of 6 M KOH, and it showed specific capacitance of 240 F g-1 at a current density of 0.5 A g-1 with excellent stability after 2000 cycles of 97% capacitance retention. Accordingly, such porous organic polymer appears to have a variety of uses in energy-related applications.
Keywords: Tröger’s base; carbazole; conjugated microporous polymer; regioselectivity; supercapacitors.