CC BY-NC-ND 4.0 · Organic Materials 2021; 03(02): 346-352
DOI: 10.1055/a-1512-5753
Energy Materials in the Age of Globalization
Original Article

Cyclotetrabenzil-Based Porous Organic Polymers with High Carbon Dioxide Affinity

a   Department of Chemistry, University of Fribourg, Chemin du Musee 9, 1700, Fribourg, Switzerland
b   Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah 23218, Saudi Arabia
c   Department of Chemistry, University of Houston, 3585 Cullen Boulevard #112, Houston, TX 77204-5003, United States
Kyung-Seob Song
a   Department of Chemistry, University of Fribourg, Chemin du Musee 9, 1700, Fribourg, Switzerland
c   Department of Chemistry, University of Houston, 3585 Cullen Boulevard #112, Houston, TX 77204-5003, United States
a   Department of Chemistry, University of Fribourg, Chemin du Musee 9, 1700, Fribourg, Switzerland
› Author Affiliations
Funding Information This project was funded by the Swiss National Science Foundation (SNF) (grant 200021-175947 to A.C.), the donors of the American Chemical Society Petroleum Research Fund (grant ND-58919 to O.Š.M.), the Welch Foundation (grant E-1768 to O.Š.M.), and the US National Science Foundation (grant DMR-1904998 to O.Š.M.).


Porous organic polymers (POPs) incorporating macrocyclic units have been investigated in recent years in an effort to transfer macrocycles' intrinsic host–guest properties onto the porous networks to achieve complex separations. In this regard, highly interesting building blocks are presented by the family of cyclotetrabenzoin macrocycles with rigid, well-defined, electron-deficient cavities. This macrocycle shows high affinity towards linear guest molecules such as carbon dioxide, thus offering an ideal building block for the synthesis of CO2-philic POPs. Herein, we report the synthesis of a POP through the condensation reaction between cyclotetrabenzil and 1,2,4,5-tetraaminobenzene under ionothermal conditions using the eutectic zinc chloride/sodium chloride/potassium chloride salt mixture at 250 °C. Notably, following the condensation reaction, the macrocycle favors three-dimensional (3D) growth rather than a two-dimensional one while retaining the cavity. The resulting polymer, named 3D-mPOP, showed a highly microporous structure with a BET surface area of 1142 m2 g−1 and a high carbon dioxide affinity with a binding enthalpy of 39 kJ mol−1. Moreover, 3D-mPOP showed very high selectivity for carbon dioxide in carbon dioxide/methane and carbon dioxide/nitrogen mixtures.

Supporting Information

Supporting Information for this article is available online at

Primary Data

Crystal structure data for octaketone have been deposited with the Cambridge Crystallographic Data Centre under code CCDC-2069402.

Supporting Information

Publication History

Received: 15 March 2021

Accepted: 25 April 2021

Accepted Manuscript online:
19 May 2021

Article published online:
24 June 2021

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