A Three‐Dimensional Porous Organic Semiconductor Based on Fully sp²‐Hybridized Graphitic Polymer

Abstract

Dimensionality plays an important role in the charge transport properties of organic semiconductors. Although three‐dimensional semiconductors, such as Si, are common in inorganic materials, imparting electrical conductivity to covalent three‐dimensional organic polymers is challenging. Now, the synthesis of a three‐dimensional π‐conjugated porous organic polymer (3D p‐POP) using catalyst‐free Diels–Alder cycloaddition polymerization followed by acid‐promoted aromatization is presented. With a surface area of 801 m2 g−1, full conjugation throughout the carbon backbone, and an electrical conductivity of 6(2)×10−4 S cm−1 upon treatment with I2 vapor, the 3D p‐POP is the first member of a new class of permanently porous 3D organic semiconductors.

Saddle‐Shaped Building Blocks: A New Concept for Designing Fully Conjugated 3D Organic Semiconducting Materials

“…However, the instability of octaketotetraphenylene and harsh reaction conditions (> 350°C) greatly limit the facile preparation and even practical applications. Later in 2020, Dincaˇand Coskun et al [27] presented an all sp 2 -hybrided carbon connected 3D π-conjugated porous organic polymer (3D p-POP), which was synthesized by catalyst-free Diels-Alder cycloaddition polymerization between the furan and 1,4-epoxynaphthalene derivatives (Figure 4b). It was found that the 3D p-POP displayed high surface area, permanent porosity, physicochemical stability and also semiconducting properties.…”

The Prospect of Dimensionality in Porous Semiconductors

“…Upon aromatization, besides an increase in the surface area, an immediate increase (two orders of magnitude) in the conductivity could be measured, whichc ould be furtheri mproved by I 2 doping to 6 10 À4 Scm À1 (Figure 5). [50]…”

Catalyst‐ and Solvent‐Free Synthesis of a Chemically Stable Aza‐Bridged Bis(phenanthroline) Macrocycle‐Linked Covalent Organic Framework

“…Even after storing the pellet in vacuum for 7 hours, the electrical conductivity slightly decreased to 2.2×10 −4 S/cm at room temperature. This result suggests that the doping state was mostly sustained in vacuum [14a, 17d] …”

“…Inspired by reports that iodine‐doping can trigger electrical conductivity in framework materials, [8a, 14a, 17b,d] the effect of iodine‐doping on the electrical conductivity of the ABBPM‐COF was studied. The iodine‐doped ABBPM‐COF powder was produced by exposing a pristine sample to iodine vapor for 8 hours.…”