Fully Conjugated Tetraoxa[8]circulene‐Based Porous Semiconducting Polymers

Abstract

Tetraoxa[8]circulenes (TOCs) are a class of hetero[8]circulenes featuring a planar cyclooctatetraene core with a mixed aromatic/antiaromatic motif that governs their electronic properties. Polymeric TOCs (pTOCs) have been the subject of several computational simulations because they are predicted to be low‐band‐gap semiconductors, but they have not been available synthetically yet. Here, we report the first example of pTOCs, a new family of porous semiconductors, synthesized under ionothermal conditions through the intermolecular cyclization of 1,4,5,8‐anthracene tetrone. pTOCs are porous, with surface areas up to 1656 m2 g−1, and exhibit light‐switchable and tunable semiconducting properties.

Using molecular straps to engineer conjugated porous polymer growth, chemical doping, and conductivity

“…Typically, electrical conductivities of doped-CPPs are measured aer pressing the powder into a pellet form. 50,51 However, for widespread use of CPPs, a simplied processing technique that allows them to process into various device congurations is required. Recently, to overcome the limitations of semiconducting polymers including environmental stability, high modulus, and processability they have been physically blended with insulating commodity polymers.…”

Fully Conjugated Benzyne‐Derived Three‐Dimensional Porous Organic Polymers

“…In order to understand the effect of the thermal treatment on the polymer structure, Raman spectra of BDP‐TChB‐200 before and after heat treatment were recorded (Figure S12). Raman spectra showed that the I D /I G ratio increased from 0.69 to 0.78 at 0.5 h of thermal treatment at 400 °C and to 0.80 at 1.0 h [21] . The I D /I G ratio continued to increase to 1.06 after 2.0 h of thermal treatment at 400 °C, which indicates increased number of defects as also suggested by the 1 H solid‐state NMR analysis of BDPs with the larger distribution of environments (Figure S11).…”

Eutectic Molten Salt Synthesis of Highly Microporous Macrocyclic Porous Organic Polymers for CO2 Capture

“…Synthesis of the POPs were performed by following our earlier reported procedures. [27,28] A Pyrex ampule was charged with powdered NaCl (82.4 mg, 1.41 mmol, 7.04 equiv. ), octaketone (106.5. mg, 0.2 mmol, 1.00 equiv.)…”

“…We also systematically investigated the effect of the reaction temperature on the textural properties of the polymers. Moreover, the traditional ZnCl 2 /NaCl/KCl eutectic mixture was also replaced with a cheaper alternative, that is AlCl 3 /NaCl eutectic molten salt mixture, [27,28] which was implemented as a reaction medium and a catalyst. The resulting 3D microporous macrocyclic POPs (3D-mmPOPs) showed surface areas up to 752 m 2 g À 1 with a micropore ratio of more than 90 %, pore volumes up to 0.32 cm 3 g À 1 and enhanced CO 2 uptake capacity of 3.51 mmol g À 1 at 273 K and 1.1 bar as well as a high CO 2 isosteric heat of adsorption, Q st , of 40.6 kJ mol À 1 at zero coverage originating from the presence of macrocyclic units.…”