Synthesis, Crystal Structure, and Luminescent Sensing Properties of a Supramolecular 3D Zinc(II) Metal–Organic Framework with Terephthalate and Bis(imidazol-1-yl)methane Linkers
Supramolecular 3D Zn(II) coordination polymer {[Zn(bim)(bdc)]⋅0.8DMF⋅0.4EtOH⋅0.1H<sub>2</sub>O }<sub>n</sub> (<b>Zn-MOF</b>), constructed from Zn<sup>2+</sup> ions, bis(imidazol-1-yl)methane (bim) and terephthalate (bdc<sup>2−</sup>) anions...
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MDPI AG
2023-06-01
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| Series: | Inorganics |
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| Online Access: | https://www.mdpi.com/2304-6740/11/7/264 |
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| author | Vladislava V. Matveevskaya Dmitry I. Pavlov Alexey A. Ryadun Vladimir P. Fedin Andrei S. Potapov |
| author_facet | Vladislava V. Matveevskaya Dmitry I. Pavlov Alexey A. Ryadun Vladimir P. Fedin Andrei S. Potapov |
| author_sort | Vladislava V. Matveevskaya |
| collection | DOAJ |
| description | Supramolecular 3D Zn(II) coordination polymer {[Zn(bim)(bdc)]⋅0.8DMF⋅0.4EtOH⋅0.1H<sub>2</sub>O }<sub>n</sub> (<b>Zn-MOF</b>), constructed from Zn<sup>2+</sup> ions, bis(imidazol-1-yl)methane (bim) and terephthalate (bdc<sup>2−</sup>) anions, was synthesized and structurally characterized. <b>Zn-MOF</b> crystallizes in the tetragonal crystal system, space group <i>P</i>4<sub>2</sub>/<i>n</i>. Each Zn(II) ion coordinates two neutral bim molecules in a bridging bidentate coordination mode via nitrogen atoms at position 3 of the imidazole rings and two bdc<sup>2−</sup> anions, with monodentate coordination of the carboxylate group for one of them and bidentate coordination for another. Zn(II) cations are in a distorted square pyramidal ZnN<sub>2</sub>O<sub>3</sub> coordination environment. Metal cations are alternately linked by the bim and bdc<sup>2−</sup> ligands, forming a two-dimensional layered structure along the crystallographic plane <i>ab</i>. As a result of layer interpenetration, a supramolecular 3D network is formed. <b>Zn-MOF</b> demonstrated blue (aquamarine) emission with a maximum at 430 nm upon excitation at 325 nm. The luminescence lifetime of 6 ns is characteristic for ligand-centered fluorescence. The luminescent sensing properties of <b>Zn-MOF</b> in ethanol suspension toward inorganic cations and anions were evaluated and an emission quenching response was observed for Fe<sup>3+</sup> and chromate/dichromate ions. Photoinduced electron transfer from <b>Zn-MOF</b> to Fe<sup>3+</sup> was elucidated as a possible quenching mechanism on the basis of DFT calculations. |
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| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-03-11T00:58:33Z |
| publishDate | 2023-06-01 |
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| spelling | doaj.art-4260369fb0644b43b3425514f279bb5d2023-11-18T19:47:37ZengMDPI AGInorganics2304-67402023-06-0111726410.3390/inorganics11070264Synthesis, Crystal Structure, and Luminescent Sensing Properties of a Supramolecular 3D Zinc(II) Metal–Organic Framework with Terephthalate and Bis(imidazol-1-yl)methane LinkersVladislava V. Matveevskaya0Dmitry I. Pavlov1Alexey A. Ryadun2Vladimir P. Fedin3Andrei S. Potapov4Nikolaev Institute of Inorganic Chemistry, 3 Lavrentiev Ave., 630090 Novosibirsk, RussiaNikolaev Institute of Inorganic Chemistry, 3 Lavrentiev Ave., 630090 Novosibirsk, RussiaNikolaev Institute of Inorganic Chemistry, 3 Lavrentiev Ave., 630090 Novosibirsk, RussiaNikolaev Institute of Inorganic Chemistry, 3 Lavrentiev Ave., 630090 Novosibirsk, RussiaNikolaev Institute of Inorganic Chemistry, 3 Lavrentiev Ave., 630090 Novosibirsk, RussiaSupramolecular 3D Zn(II) coordination polymer {[Zn(bim)(bdc)]⋅0.8DMF⋅0.4EtOH⋅0.1H<sub>2</sub>O }<sub>n</sub> (<b>Zn-MOF</b>), constructed from Zn<sup>2+</sup> ions, bis(imidazol-1-yl)methane (bim) and terephthalate (bdc<sup>2−</sup>) anions, was synthesized and structurally characterized. <b>Zn-MOF</b> crystallizes in the tetragonal crystal system, space group <i>P</i>4<sub>2</sub>/<i>n</i>. Each Zn(II) ion coordinates two neutral bim molecules in a bridging bidentate coordination mode via nitrogen atoms at position 3 of the imidazole rings and two bdc<sup>2−</sup> anions, with monodentate coordination of the carboxylate group for one of them and bidentate coordination for another. Zn(II) cations are in a distorted square pyramidal ZnN<sub>2</sub>O<sub>3</sub> coordination environment. Metal cations are alternately linked by the bim and bdc<sup>2−</sup> ligands, forming a two-dimensional layered structure along the crystallographic plane <i>ab</i>. As a result of layer interpenetration, a supramolecular 3D network is formed. <b>Zn-MOF</b> demonstrated blue (aquamarine) emission with a maximum at 430 nm upon excitation at 325 nm. The luminescence lifetime of 6 ns is characteristic for ligand-centered fluorescence. The luminescent sensing properties of <b>Zn-MOF</b> in ethanol suspension toward inorganic cations and anions were evaluated and an emission quenching response was observed for Fe<sup>3+</sup> and chromate/dichromate ions. Photoinduced electron transfer from <b>Zn-MOF</b> to Fe<sup>3+</sup> was elucidated as a possible quenching mechanism on the basis of DFT calculations.https://www.mdpi.com/2304-6740/11/7/264zincmetal–organic frameworkbis(imidazol-1-yl)methaneterephthalic acidcrystal structureluminescence |
| spellingShingle | Vladislava V. Matveevskaya Dmitry I. Pavlov Alexey A. Ryadun Vladimir P. Fedin Andrei S. Potapov Synthesis, Crystal Structure, and Luminescent Sensing Properties of a Supramolecular 3D Zinc(II) Metal–Organic Framework with Terephthalate and Bis(imidazol-1-yl)methane Linkers Inorganics zinc metal–organic framework bis(imidazol-1-yl)methane terephthalic acid crystal structure luminescence |
| title | Synthesis, Crystal Structure, and Luminescent Sensing Properties of a Supramolecular 3D Zinc(II) Metal–Organic Framework with Terephthalate and Bis(imidazol-1-yl)methane Linkers |
| title_full | Synthesis, Crystal Structure, and Luminescent Sensing Properties of a Supramolecular 3D Zinc(II) Metal–Organic Framework with Terephthalate and Bis(imidazol-1-yl)methane Linkers |
| title_fullStr | Synthesis, Crystal Structure, and Luminescent Sensing Properties of a Supramolecular 3D Zinc(II) Metal–Organic Framework with Terephthalate and Bis(imidazol-1-yl)methane Linkers |
| title_full_unstemmed | Synthesis, Crystal Structure, and Luminescent Sensing Properties of a Supramolecular 3D Zinc(II) Metal–Organic Framework with Terephthalate and Bis(imidazol-1-yl)methane Linkers |
| title_short | Synthesis, Crystal Structure, and Luminescent Sensing Properties of a Supramolecular 3D Zinc(II) Metal–Organic Framework with Terephthalate and Bis(imidazol-1-yl)methane Linkers |
| title_sort | synthesis crystal structure and luminescent sensing properties of a supramolecular 3d zinc ii metal organic framework with terephthalate and bis imidazol 1 yl methane linkers |
| topic | zinc metal–organic framework bis(imidazol-1-yl)methane terephthalic acid crystal structure luminescence |
| url | https://www.mdpi.com/2304-6740/11/7/264 |
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