Dication Containing Three Aromatic Ring Structure-Directs toward a Chiral Zeolite, Spans Three Cavities, and Effectively Traps Water
| Autor: | Zihao Rei Gao, Salvador R. G. Balestra, Luis Gómez-Hortigüela, Jian Li, Carlos Márquez-Alvarez, Miguel A. Camblor |
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| Přispěvatelé: | Ministerio de Ciencia e Innovación (España), Agencia Estatal de Investigación (España), Balestra, Salvador R. G., Gómez-Hortigüela Sainz, Luis, Li, Jian, Márquez Álvarez, Carlos, Camblor, Miguel Ángel, Gao, Zihao Rei, Balestra, Salvador R. G. [0000-0002-2163-2782], Gómez-Hortigüela Sainz, Luis [0000-0002-4960-8709], Li, Jian [0000-0003-2221-2285], Márquez Álvarez, Carlos [0000-0003-2749-4269], Camblor, Miguel Ángel [0000-0001-9591-3432], Gao, Zihao Rei [0000-0003-0331-3515] |
| Jazyk: | angličtina |
| Rok vydání: | 2022 |
| Předmět: | |
| Zdroj: | Digital.CSIC. Repositorio Institucional del CSIC instname |
| Popis: | [EN] The chiral zeolite STW has been synthesized using a large dication containing three aromatic rings (two imidazolium moieties plus a benzene one). The integrity of the occluded organics is proven by 1H and 13C liquid NMR of the zeolite dissolved in HF/D2O. Molecular simulations strongly suggest that each aromatic ring is located in a different cavity so that each dication crosses two medium pore 10-membered-ring (MR) windows. This is confirmed by Rietveld refinement against synchrotron powder X-ray diffraction data, which suggests that there is also trapped water in the cavities, explaining a significant excess of H found in this material. The presence of water is very soundly confirmed by Fourier-transform infrared experiments, which also show that this water cannot leave the zeolite even after heating at 180 °C under vacuum. Molecular simulations allow us to conclude that this is due to the blockage of the 10 and 8MR windows by the occluded organics. The peculiar situation of an organic structure-directing agent spanning three cavities has important implications for the structure-direction concept that are briefly discussed. Several chiral derivatives of this dication have also been studied, and their possibility to enantioselectively direct the crystallization of STW has been analyzed. This article is part of projects PID2019-105479RB-I00 and PID2019-107968RB-I00 funded by MCIN/AEI/10.13039/501100011033, Spain. S.R.G.B. was supported by grant FJC2018-035697-I funded by MCIN/AEI/10.13039/501100011033. Centro Técnico Informático-CSIC, Trueno, and CESGA (Supercomputing Center of Galicia) cluster facilities are acknowledged for running the calculations. OpenAccess funding is provided by CSIC. |
| Databáze: | OpenAIRE |
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