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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...

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Autores principales: Kumar, Kunal, Stefanczyk, Olaf, Nakabayashi, Koji, Mineo, Yuuki, Ohkoshi, Shin-ichi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2022
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.
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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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