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Development of Nd (III)-Based Terahertz Absorbers Revealing Temperature Dependent Near-Infrared Luminescence
Molecular vibrations in the solid-state, detectable in the terahertz (THz) region, are the subject of research to further develop THz technologies. To observe such vibrations in terahertz time-domain spectroscopy (THz-TDS) and low-frequency (LF) Raman spectroscopy, two supramolecular assemblies with...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9181137/ https://www.ncbi.nlm.nih.gov/pubmed/35682730 http://dx.doi.org/10.3390/ijms23116051 |
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author | Kumar, Kunal Stefanczyk, Olaf Nakabayashi, Koji Mineo, Yuuki Ohkoshi, Shin-ichi |
author_facet | Kumar, Kunal Stefanczyk, Olaf Nakabayashi, Koji Mineo, Yuuki Ohkoshi, Shin-ichi |
author_sort | Kumar, Kunal |
collection | PubMed |
description | Molecular vibrations in the solid-state, detectable in the terahertz (THz) region, are the subject of research to further develop THz technologies. To observe such vibrations in terahertz time-domain spectroscopy (THz-TDS) and low-frequency (LF) Raman spectroscopy, two supramolecular assemblies with the formula [Nd(III) (phen)(3) (NCX)(3)] 0.3EtOH (X = S, 1-S; Se, 1-Se) were designed and prepared. Both compounds show several THz-TDS and LF-Raman peaks in the sub-THz range, with the lowest frequencies of 0.65 and 0.59 THz for 1-S and 1-Se, and 0.75 and 0.61 THz for 1-S and 1-Se, respectively. The peak redshift was observed due to the substitution of SCN(−) by SeCN(−). Additionally, temperature-dependent TDS-THz studies showed a thermal blueshift phenomenon, as the peak position shifted to 0.68 THz for 1-S and 0.62 THz for 1-Se at 10 K. Based on ab initio calculations, sub-THz vibrations were ascribed to the swaying of the three thiocyanate/selenocyanate. Moreover, both samples exhibited near-infrared (NIR) emission from Nd (III), and very good thermometric properties in the 300–150 K range, comparable to neodymium (III) oxide-based thermometers and higher than previously reported complexes. Moreover, the temperature dependence of fluorescence and THz spectroscopy analysis showed that the reduction in anharmonic thermal vibrations leads to a significant increase in the intensity and a reduction in the width of the emission and LF absorption peaks. These studies provide the basis for developing new routes to adjust the LF vibrational absorption. |
format | Online Article Text |
id | pubmed-9181137 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-91811372022-06-10 Development of Nd (III)-Based Terahertz Absorbers Revealing Temperature Dependent Near-Infrared Luminescence Kumar, Kunal Stefanczyk, Olaf Nakabayashi, Koji Mineo, Yuuki Ohkoshi, Shin-ichi Int J Mol Sci Article Molecular vibrations in the solid-state, detectable in the terahertz (THz) region, are the subject of research to further develop THz technologies. To observe such vibrations in terahertz time-domain spectroscopy (THz-TDS) and low-frequency (LF) Raman spectroscopy, two supramolecular assemblies with the formula [Nd(III) (phen)(3) (NCX)(3)] 0.3EtOH (X = S, 1-S; Se, 1-Se) were designed and prepared. Both compounds show several THz-TDS and LF-Raman peaks in the sub-THz range, with the lowest frequencies of 0.65 and 0.59 THz for 1-S and 1-Se, and 0.75 and 0.61 THz for 1-S and 1-Se, respectively. The peak redshift was observed due to the substitution of SCN(−) by SeCN(−). Additionally, temperature-dependent TDS-THz studies showed a thermal blueshift phenomenon, as the peak position shifted to 0.68 THz for 1-S and 0.62 THz for 1-Se at 10 K. Based on ab initio calculations, sub-THz vibrations were ascribed to the swaying of the three thiocyanate/selenocyanate. Moreover, both samples exhibited near-infrared (NIR) emission from Nd (III), and very good thermometric properties in the 300–150 K range, comparable to neodymium (III) oxide-based thermometers and higher than previously reported complexes. Moreover, the temperature dependence of fluorescence and THz spectroscopy analysis showed that the reduction in anharmonic thermal vibrations leads to a significant increase in the intensity and a reduction in the width of the emission and LF absorption peaks. These studies provide the basis for developing new routes to adjust the LF vibrational absorption. MDPI 2022-05-27 /pmc/articles/PMC9181137/ /pubmed/35682730 http://dx.doi.org/10.3390/ijms23116051 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Kumar, Kunal Stefanczyk, Olaf Nakabayashi, Koji Mineo, Yuuki Ohkoshi, Shin-ichi Development of Nd (III)-Based Terahertz Absorbers Revealing Temperature Dependent Near-Infrared Luminescence |
title | Development of Nd (III)-Based Terahertz Absorbers Revealing Temperature Dependent Near-Infrared Luminescence |
title_full | Development of Nd (III)-Based Terahertz Absorbers Revealing Temperature Dependent Near-Infrared Luminescence |
title_fullStr | Development of Nd (III)-Based Terahertz Absorbers Revealing Temperature Dependent Near-Infrared Luminescence |
title_full_unstemmed | Development of Nd (III)-Based Terahertz Absorbers Revealing Temperature Dependent Near-Infrared Luminescence |
title_short | Development of Nd (III)-Based Terahertz Absorbers Revealing Temperature Dependent Near-Infrared Luminescence |
title_sort | development of nd (iii)-based terahertz absorbers revealing temperature dependent near-infrared luminescence |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9181137/ https://www.ncbi.nlm.nih.gov/pubmed/35682730 http://dx.doi.org/10.3390/ijms23116051 |
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