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Polymers 2018, 10(12), 1398;

Paddlewheel SBU based Zn MOFs: Syntheses, Structural Diversity, and CO2 Adsorption Properties

Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan
Department of Chemistry and Biochemistry, National Chung Cheng University, Chiayi 621, Taiwan
Department of Applied Chemistry, National Chi Nan University, Nantou 545, Taiwan
Authors to whom correspondence should be addressed.
Received: 15 November 2018 / Revised: 14 December 2018 / Accepted: 14 December 2018 / Published: 17 December 2018
(This article belongs to the Special Issue Advances in Coordination Polymers)
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Four Zn metal–organic frameworks (MOFs), {[Zn2(2,6-ndc)2(2-Pn)]·DMF}n (1), {[Zn2(cca)2(2-Pn)]·DMF}n (2), {[Zn2(thdc)2(2-Pn)]·3DMF}n (3), and {[Zn2(1,4-ndc)2(2-Pn)]·1.5DMF}n (4), were synthesized from zinc nitrate and N,N′-bis(pyridin-2-yl)benzene-1,4-diamine (2-Pn) with naphthalene-2,6-dicarboxylic acid (2,6-H2ndc), 4-carboxycinnamic acid (H2cca), 2,5-thiophenedicarboxylic acid (H2thdc), and naphthalene-1,4-dicarboxylic acid (1,4-H2ndc), respectively. MOFs 14 were all constructed from similar dinuclear paddlewheel {Zn2(COO)4} clusters and resulted in the formation of three kinds of uninodal 6-connected non-interpenetrated frameworks. MOFs 1 and 2 suit a topologic 48·67-net with 17.6% and 16.8% extra-framework voids, respectively, 3 adopts a pillared-layer open framework of 48·66·8-topology with sufficient free voids of 39.9%, and 4 features a pcu-type pillared-layer framework of 412·63-topology with sufficient free voids of 30.9%. CO2 sorption studies exhibited typical reversible type I isotherms with CO2 uptakes of 55.1, 84.6, and 64.3 cm3 g−1 at 195 K and P/P0 =1 for the activated materials 1′, 2′, and 4′, respectively. The coverage-dependent isosteric heat of CO2 adsorption (Qst) gave commonly decreased Qst traces with increasing CO2 uptake for all the three materials and showed an adsorption enthalpy of 32.5 kJ mol−1 for 1′, 38.3 kJ mol−1 for 2′, and 23.5 kJ mol−1 for 4′ at zero coverage. View Full-Text
Keywords: CO2 adsorption; metal–organic framework; secondary building unit; zinc CO2 adsorption; metal–organic framework; secondary building unit; zinc

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Lin, T.-R.; Lee, C.-H.; Lan, Y.-C.; Mendiratta, S.; Lai, L.-L.; Wu, J.-Y.; Chi, K.-M.; Lu, K.-L. Paddlewheel SBU based Zn MOFs: Syntheses, Structural Diversity, and CO2 Adsorption Properties. Polymers 2018, 10, 1398.

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