Quinoid-Thiophene-Based Covalent Organic Polymers for High Iodine Uptake: When Rational Chemical Design...

A novel 2D covalent organic polymer (COP), based on conjugated quinoid-oligothiophene (QOT) and tris(aminophenyl) benzene (TAPB) moieties, is designed and synthesized (TAPB-QOT COP). Some DFT calculations are made to clarify the equilibrium between different QOT isomers and how they could affect the COP formation. Once synthetized, the polymer has been thoroughly characterized by spectroscopic (i.e., Raman, UV-vis), SSNMR and surface (e.g., SEM, BET) techniques, showing a modest surface area (113 m² g^-1) and micropore volume (0.014 cm³ g^-1 with an averaged pore size of 5.6-8 Å). Notwithstanding this, TAPB-QOT COP shows a remarkably high iodine (I₂) uptake capacity (464 %wt) comparable to or even higher than state-of-the-art porous organic polymers (POPs). These auspicious values are due to the thoughtful design of the polymer with embedded sulfur sites and a conjugated scaffold with the ability to counterbalance the relatively low pore volumes. Indeed, both morphological and Raman data, supported by computational analyses, prove the very high affinity between the S atom in our COP and the I₂. As a result, TAPB-QOT COP shows the highest volumetric I₂ uptake (i.e., the amount of I₂ uptaken per volume unit) up to 331 g cm^-3 coupled with a remarkably high reversibility (>80% after five cycles).