Self-Assembly of a Two-Dimensional Coordination Polymer Based on Silver and Lanthanide Tetrakis-Acylpyrazolonates: An Efficient New Strategy for Suppressing Ligand-to-Metal Charge Transfer Quenching of Europium Luminescence
A new strategy for the easy polymerization of anionic [Ln(Q<sup>cy</sup>)<sub>4</sub>]<sup>−</sup> (HQ<sup>cy</sup>-4-(cyclohexanecarbonyl)-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one) into two-dimensional layers of [AgLn(Q<sup>cy</sup>)...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-02-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/15/4/867 |
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| author | Yury A. Belousov Mikhail T. Metlin Darya A. Metlina Mikhail A. Kiskin Ilya A. Yakushev Trofim A. Polikovskiy Ilya V. Taydakov Andrei A. Drozdov Fabio Marchetti Claudio Pettinari |
| author_facet | Yury A. Belousov Mikhail T. Metlin Darya A. Metlina Mikhail A. Kiskin Ilya A. Yakushev Trofim A. Polikovskiy Ilya V. Taydakov Andrei A. Drozdov Fabio Marchetti Claudio Pettinari |
| author_sort | Yury A. Belousov |
| collection | DOAJ |
| description | A new strategy for the easy polymerization of anionic [Ln(Q<sup>cy</sup>)<sub>4</sub>]<sup>−</sup> (HQ<sup>cy</sup>-4-(cyclohexanecarbonyl)-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one) into two-dimensional layers of [AgLn(Q<sup>cy</sup>)<sub>4</sub>]<sub>n</sub> (Ln = Sm, Eu, Gd, Tb and Dy) is proposed by binding the single molecular anions [Ln(Q<sup>cy</sup>)<sub>4</sub>]<sup>−</sup> to silver cations through the coordination of the pyridinic nitrogen atoms of the pyrazolonate rings. The luminescent properties of [AgLn(Q<sup>cy</sup>)<sub>4</sub>]<sub>n</sub> have been studied in detail, and it was shown that the previously described low photoluminescence quantum yield (PLQY) of [Eu(Q<sup>cy</sup>)<sub>4</sub>]<sup>−</sup> is due to Ligand-To-Metal Charge Transfer (LMCT) quenching, which is effectively suppressed in the heterometallic [AgEu(Q<sup>cy</sup>)<sub>4</sub>]<sub>n</sub> polymer. Sensibilization coefficients for H<sub>3</sub>O[Eu(Q<sup>cy</sup>)<sub>4</sub>], [AgEu(Q<sup>cy</sup>)<sub>4</sub>]<sub>n</sub>, and H<sub>3</sub>O[Sm(Q<sup>cy</sup>)<sub>4</sub>] complexes (n ≈ 1) were estimated via theoretical analysis (also by using Judd-Ofelt theory for Sm<sup>3+</sup>) and PLQY measurements. |
| first_indexed | 2024-03-11T08:14:08Z |
| format | Article |
| id | doaj.art-c1867bcab1de4dd3977e423cb6794f26 |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-11T08:14:08Z |
| publishDate | 2023-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-c1867bcab1de4dd3977e423cb6794f262023-11-16T22:51:01ZengMDPI AGPolymers2073-43602023-02-0115486710.3390/polym15040867Self-Assembly of a Two-Dimensional Coordination Polymer Based on Silver and Lanthanide Tetrakis-Acylpyrazolonates: An Efficient New Strategy for Suppressing Ligand-to-Metal Charge Transfer Quenching of Europium LuminescenceYury A. Belousov0Mikhail T. Metlin1Darya A. Metlina2Mikhail A. Kiskin3Ilya A. Yakushev4Trofim A. Polikovskiy5Ilya V. Taydakov6Andrei A. Drozdov7Fabio Marchetti8Claudio Pettinari9Chemistry Department, M.V. Lomonosov Moscow State University, Leninskie Gory Str, Building 1/3, 119991 Moscow, RussiaP. N. Lebedev Physical Institute of Russian Academy of Sciences, Leninsky Prospect 53, 119991 Moscow, RussiaP. N. Lebedev Physical Institute of Russian Academy of Sciences, Leninsky Prospect 53, 119991 Moscow, RussiaKurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Leninsky Prospekt 31, 119991 Moscow, RussiaKurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Leninsky Prospekt 31, 119991 Moscow, RussiaP. N. Lebedev Physical Institute of Russian Academy of Sciences, Leninsky Prospect 53, 119991 Moscow, RussiaP. N. Lebedev Physical Institute of Russian Academy of Sciences, Leninsky Prospect 53, 119991 Moscow, RussiaChemistry Department, M.V. Lomonosov Moscow State University, Leninskie Gory Str, Building 1/3, 119991 Moscow, RussiaSchool of Science and Tecnology, Chemistry Interdisciplinary Project (ChIP), University of Camerino, Via Madonna delle Carceri, 62032 Camerino, ItalySchool of Pharmacy, Chemistry Interdisciplinary Project (ChIP), University of Camerino, Via Madonna delle Carceri, 62032 Camerino, ItalyA new strategy for the easy polymerization of anionic [Ln(Q<sup>cy</sup>)<sub>4</sub>]<sup>−</sup> (HQ<sup>cy</sup>-4-(cyclohexanecarbonyl)-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one) into two-dimensional layers of [AgLn(Q<sup>cy</sup>)<sub>4</sub>]<sub>n</sub> (Ln = Sm, Eu, Gd, Tb and Dy) is proposed by binding the single molecular anions [Ln(Q<sup>cy</sup>)<sub>4</sub>]<sup>−</sup> to silver cations through the coordination of the pyridinic nitrogen atoms of the pyrazolonate rings. The luminescent properties of [AgLn(Q<sup>cy</sup>)<sub>4</sub>]<sub>n</sub> have been studied in detail, and it was shown that the previously described low photoluminescence quantum yield (PLQY) of [Eu(Q<sup>cy</sup>)<sub>4</sub>]<sup>−</sup> is due to Ligand-To-Metal Charge Transfer (LMCT) quenching, which is effectively suppressed in the heterometallic [AgEu(Q<sup>cy</sup>)<sub>4</sub>]<sub>n</sub> polymer. Sensibilization coefficients for H<sub>3</sub>O[Eu(Q<sup>cy</sup>)<sub>4</sub>], [AgEu(Q<sup>cy</sup>)<sub>4</sub>]<sub>n</sub>, and H<sub>3</sub>O[Sm(Q<sup>cy</sup>)<sub>4</sub>] complexes (n ≈ 1) were estimated via theoretical analysis (also by using Judd-Ofelt theory for Sm<sup>3+</sup>) and PLQY measurements.https://www.mdpi.com/2073-4360/15/4/867lanthanidesluminescenceLMCT quenchingsilverpyrazolonateseuropium |
| spellingShingle | Yury A. Belousov Mikhail T. Metlin Darya A. Metlina Mikhail A. Kiskin Ilya A. Yakushev Trofim A. Polikovskiy Ilya V. Taydakov Andrei A. Drozdov Fabio Marchetti Claudio Pettinari Self-Assembly of a Two-Dimensional Coordination Polymer Based on Silver and Lanthanide Tetrakis-Acylpyrazolonates: An Efficient New Strategy for Suppressing Ligand-to-Metal Charge Transfer Quenching of Europium Luminescence Polymers lanthanides luminescence LMCT quenching silver pyrazolonates europium |
| title | Self-Assembly of a Two-Dimensional Coordination Polymer Based on Silver and Lanthanide Tetrakis-Acylpyrazolonates: An Efficient New Strategy for Suppressing Ligand-to-Metal Charge Transfer Quenching of Europium Luminescence |
| title_full | Self-Assembly of a Two-Dimensional Coordination Polymer Based on Silver and Lanthanide Tetrakis-Acylpyrazolonates: An Efficient New Strategy for Suppressing Ligand-to-Metal Charge Transfer Quenching of Europium Luminescence |
| title_fullStr | Self-Assembly of a Two-Dimensional Coordination Polymer Based on Silver and Lanthanide Tetrakis-Acylpyrazolonates: An Efficient New Strategy for Suppressing Ligand-to-Metal Charge Transfer Quenching of Europium Luminescence |
| title_full_unstemmed | Self-Assembly of a Two-Dimensional Coordination Polymer Based on Silver and Lanthanide Tetrakis-Acylpyrazolonates: An Efficient New Strategy for Suppressing Ligand-to-Metal Charge Transfer Quenching of Europium Luminescence |
| title_short | Self-Assembly of a Two-Dimensional Coordination Polymer Based on Silver and Lanthanide Tetrakis-Acylpyrazolonates: An Efficient New Strategy for Suppressing Ligand-to-Metal Charge Transfer Quenching of Europium Luminescence |
| title_sort | self assembly of a two dimensional coordination polymer based on silver and lanthanide tetrakis acylpyrazolonates an efficient new strategy for suppressing ligand to metal charge transfer quenching of europium luminescence |
| topic | lanthanides luminescence LMCT quenching silver pyrazolonates europium |
| url | https://www.mdpi.com/2073-4360/15/4/867 |
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