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Triazatruxene-Based Ordered Porous Polymer: High Capacity CO2, CH4, and H-2 Capture, Heterogeneous Suzuki-Miyaura Catalytic Coupling, and Thermoelectric Properties

Sadak, Ali Enis; Karakus, Erman; Chumakov, Yurii M.; Dogan, Nesibe A.; Yavuz, Cafer T.


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    <subfield code="a">A hypercrosslinked ultramicroporous and ordered organic polymer network was synthesized from a planar trimer indole building block called triazatruxene (TAT) through anhydrous FeCl3 catalyzed Friedel-Crafts alkylation using methylal as a crosslinker. The polymer network is stable in a variety of chemicals and thermally durable. The hypercrosslinked network TATHCP shows a high BET (Brunauer-Emmet-Teller) specific surface area of 997 m(2) g(-1) with CO2 uptake capacity of 12.55 wt % at 273 K, 1.1 bar. Gas selectivities of 38.4 for CO2/N-2, 7.8 for CO2/CH4, 40.6 for CO2/O-2, and 32.1 for CO2/CO were achieved through IAST calculation. The PXRD analysis has revealed that TATHCP has a fully eclipsed structure in full agreement with Pawley refinement. The ordered 2D layers provide anisotropy that could be used in catalysis and thermoelectric measurements. After loading with Pd(II), TATHCP-Pd showed high catalytic activity in Suzuki-Miyaura cross coupling reaction with a wide range of reagents and excellent reaction yields of 90-98% with good recyclability. The structure of TATHCP-Pd was found to have two independent molecules of Pd(OAc)(2) in the asymmetric unit cell which are arranged between two TATHCP layers. Thermoelectric properties of TATHCP showed a high Seebeck coefficient and ZT, a first and promising example in HCPs with applications in all-organic thermal energy recovery devices.</subfield>
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