Luminescent Properties of Phosphonate Ester-Supported Neodymium(III) Nitrate and Chloride Complexes
This study examines the synthesis of two geminal bisphosphonate ester-supported Ln<sup>3+</sup> complexes [Ln(<b>L3</b>)<sub>2</sub>(NO<sub>3</sub>)<sub>3</sub>] (Ln = Nd<sup>3+</sup> (<b>5</b>), La<sup>3+</...
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MDPI AG
2022-12-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/1/48 |
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| author | Miriam Gerstel Ingo Koehne Johann Peter Reithmaier Rudolf Pietschnig Mohamed Benyoucef |
| author_facet | Miriam Gerstel Ingo Koehne Johann Peter Reithmaier Rudolf Pietschnig Mohamed Benyoucef |
| author_sort | Miriam Gerstel |
| collection | DOAJ |
| description | This study examines the synthesis of two geminal bisphosphonate ester-supported Ln<sup>3+</sup> complexes [Ln(<b>L3</b>)<sub>2</sub>(NO<sub>3</sub>)<sub>3</sub>] (Ln = Nd<sup>3+</sup> (<b>5</b>), La<sup>3+</sup> (<b>6</b>)) and optical properties of the neodymium(III) complex. These results are compared to known mono-phosphonate ester-based Nd<sup>3+</sup> complexes [Nd(<b>L1</b>/<b>L2</b>)<sub>3</sub>X<sub>3</sub>]<sub>n</sub> (X = NO<sub>3</sub><sup>−</sup>, n = 1; Cl<sup>−</sup>, n = 2) (<b>1</b>–<b>4</b>). The optical properties of Nd<sup>3+</sup> compounds are determined by micro-photoluminescence (µ-PL) spectroscopy which reveals three characteristic metal-centered emission bands in the NIR region related to transitions from <sup>4</sup>F<sub>3/2</sub> excited state. Additionally, two emission bands from <sup>4</sup>F<sub>5/2</sub>, <sup>2</sup>H<sub>9/2</sub> → <sup>4</sup>I<sub>J</sub> (J = 11/2, 13/2) transitions were observed. PL spectroscopy of equimolar complex solutions in dry dichloromethane (DCM) revealed remarkably higher emission intensity of the mono-phosphonate ester-based complexes in comparison to their bisphosphonate ester congener. The temperature-dependent PL measurements enable assignment of the emission lines of the <sup>4</sup>F<sub>3/2</sub> → <sup>4</sup>I<sub>9/2</sub> transition. Furthermore, low-temperature polarization-dependent measurements of the transitions from R<sub>1</sub> and R<sub>2</sub> Stark sublevel of <sup>4</sup>F<sub>3/2</sub> state to the <sup>4</sup>I<sub>9/2</sub> state for crystals of [Nd(<b>L3</b>)<sub>2</sub>(NO<sub>3</sub>)<sub>3</sub>] (<b>5</b>) are discussed. |
| first_indexed | 2024-03-09T12:07:17Z |
| format | Article |
| id | doaj.art-094ac3e51e134ac88b0c078dad436904 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T12:07:17Z |
| publishDate | 2022-12-01 |
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| spelling | doaj.art-094ac3e51e134ac88b0c078dad4369042023-11-30T22:56:14ZengMDPI AGMolecules1420-30492022-12-012814810.3390/molecules28010048Luminescent Properties of Phosphonate Ester-Supported Neodymium(III) Nitrate and Chloride ComplexesMiriam Gerstel0Ingo Koehne1Johann Peter Reithmaier2Rudolf Pietschnig3Mohamed Benyoucef4Institute of Nanostructure Technologies and Analytics (INA) and CINSaT, University of Kassel, Heinrich-Plett-Str. 40, 34132 Kassel, GermanyInstitute of Chemistry and Center for Interdisciplinary Nanostructure Science and Technology (CINSaT), University of Kassel, Heinrich-Plett-Str. 40, 34132 Kassel, GermanyInstitute of Nanostructure Technologies and Analytics (INA) and CINSaT, University of Kassel, Heinrich-Plett-Str. 40, 34132 Kassel, GermanyInstitute of Chemistry and Center for Interdisciplinary Nanostructure Science and Technology (CINSaT), University of Kassel, Heinrich-Plett-Str. 40, 34132 Kassel, GermanyInstitute of Nanostructure Technologies and Analytics (INA) and CINSaT, University of Kassel, Heinrich-Plett-Str. 40, 34132 Kassel, GermanyThis study examines the synthesis of two geminal bisphosphonate ester-supported Ln<sup>3+</sup> complexes [Ln(<b>L3</b>)<sub>2</sub>(NO<sub>3</sub>)<sub>3</sub>] (Ln = Nd<sup>3+</sup> (<b>5</b>), La<sup>3+</sup> (<b>6</b>)) and optical properties of the neodymium(III) complex. These results are compared to known mono-phosphonate ester-based Nd<sup>3+</sup> complexes [Nd(<b>L1</b>/<b>L2</b>)<sub>3</sub>X<sub>3</sub>]<sub>n</sub> (X = NO<sub>3</sub><sup>−</sup>, n = 1; Cl<sup>−</sup>, n = 2) (<b>1</b>–<b>4</b>). The optical properties of Nd<sup>3+</sup> compounds are determined by micro-photoluminescence (µ-PL) spectroscopy which reveals three characteristic metal-centered emission bands in the NIR region related to transitions from <sup>4</sup>F<sub>3/2</sub> excited state. Additionally, two emission bands from <sup>4</sup>F<sub>5/2</sub>, <sup>2</sup>H<sub>9/2</sub> → <sup>4</sup>I<sub>J</sub> (J = 11/2, 13/2) transitions were observed. PL spectroscopy of equimolar complex solutions in dry dichloromethane (DCM) revealed remarkably higher emission intensity of the mono-phosphonate ester-based complexes in comparison to their bisphosphonate ester congener. The temperature-dependent PL measurements enable assignment of the emission lines of the <sup>4</sup>F<sub>3/2</sub> → <sup>4</sup>I<sub>9/2</sub> transition. Furthermore, low-temperature polarization-dependent measurements of the transitions from R<sub>1</sub> and R<sub>2</sub> Stark sublevel of <sup>4</sup>F<sub>3/2</sub> state to the <sup>4</sup>I<sub>9/2</sub> state for crystals of [Nd(<b>L3</b>)<sub>2</sub>(NO<sub>3</sub>)<sub>3</sub>] (<b>5</b>) are discussed.https://www.mdpi.com/1420-3049/28/1/48photoluminescence spectroscopylanthanidephosphonate ester ligandsneodymiumX-ray |
| spellingShingle | Miriam Gerstel Ingo Koehne Johann Peter Reithmaier Rudolf Pietschnig Mohamed Benyoucef Luminescent Properties of Phosphonate Ester-Supported Neodymium(III) Nitrate and Chloride Complexes Molecules photoluminescence spectroscopy lanthanide phosphonate ester ligands neodymium X-ray |
| title | Luminescent Properties of Phosphonate Ester-Supported Neodymium(III) Nitrate and Chloride Complexes |
| title_full | Luminescent Properties of Phosphonate Ester-Supported Neodymium(III) Nitrate and Chloride Complexes |
| title_fullStr | Luminescent Properties of Phosphonate Ester-Supported Neodymium(III) Nitrate and Chloride Complexes |
| title_full_unstemmed | Luminescent Properties of Phosphonate Ester-Supported Neodymium(III) Nitrate and Chloride Complexes |
| title_short | Luminescent Properties of Phosphonate Ester-Supported Neodymium(III) Nitrate and Chloride Complexes |
| title_sort | luminescent properties of phosphonate ester supported neodymium iii nitrate and chloride complexes |
| topic | photoluminescence spectroscopy lanthanide phosphonate ester ligands neodymium X-ray |
| url | https://www.mdpi.com/1420-3049/28/1/48 |
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