The methylene spacer matters: the structural and luminescent effects of positional isomerism of n-methylpyridyltriazole carboxylate semi-rigid ligands in the structure of Zn(II) based coordination polymers
Entity
UAM. Departamento de Química InorgánicaPublisher
MDPIDate
2023-02-10Citation
10.3390/polym15040888
Polymers 15.4 (2023): 888
ISSN
2073-4360 (online)DOI
10.3390/polym15040888Editor's Version
https://doi.org/10.3390/polym15040888Subjects
Coordination polymers; Luminescence; Metal-organic framework; QuímicaRights
© 2023 by the authorsAbstract
Two Zn(II) coordination polymers (CPs) based on n-methylpyridyltriazole carboxylate semi-rigid organic ligands (n-MPTC), with n = 3 (L1) and 4 (L2), have been prepared at the water n-butanol interphase by reacting Zn(NO3)2·4H2O with NaL1 and NaL2. This allows us to systematically investigate the influence of the isomeric positional effect on their structures. The organic ligands were obtained by saponification from their respective ester precursors ethyl-5-methyl-1-(pyridin-3-ylmethyl)-1H-1,2,3-triazole-4-carboxylate (P1) and ethyl-5-methyl-1-(pyridin-4-ylmethyl)-1H-1,2,3-triazole-4-carboxylate (P2), resulting in their corresponding sodium salt forms, 3-MPTC, and 4-MPTC. The structure of the Zn(II) CPs determined by single-crystal X-ray diffraction reveals that both CPs have 2D supramolecular hydrogen bond networks. The 2D supramolecular network of [Zn(L1)]n (1) is built up by hydrogen bond interactions between oxygen and hydrogen atoms between neighboring n-methylpyridyltriazole molecules, whereas in [Zn(L2)·4H2O]n (2) the water molecules link 1D polymeric chains forming a 2D supramolecular aggregate. The structures of 1 and 2 clearly show that the isomeric effect in the semi-rigid ligands plays a vital role in constructing the Zn(II) coordination polymers, helped by the presence of the methylene spacer group, in the final structural conformation. The structures of 1 and 2 significantly affect their luminescent properties. Thus, while 2 shows strong emission at room temperature centered at 367 nm, the emission of 1 is quenched substantially
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Google Scholar:Narea, Pilar
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Hernández, Benjamín
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Cisterna, Jonathan
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Cárdenas, Alejandro
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Amo Ochoa, María Pilar
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Zamora Abanades, Félix Juan
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Delgado, Gerzon E.
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Llanos, Jaime
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Brito, Iván
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