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Insights into the Effect of Trans-to-Cis Photoisomerization of a Co-coordinated Stilbene Derivative on the Luminescence of Di-β-diketonate Lanthanide Complexes
[Image: see text] Five lanthanide complexes constructed from a stilbene derivative, (E)-N′,N′-bis(pyridin-2-ylmethyl)-4-styrylbenzoyl hydrazide (HL), and two β-diketonates (2-thenoyltrifluoroacetonate, tta), with or without a trifluoroacetate anion (CF(3)CO(2)(–)), namely, [Ln(tta)(2)(HL) (CF(3)CO(2...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2021
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8757447/ https://www.ncbi.nlm.nih.gov/pubmed/35036758 http://dx.doi.org/10.1021/acsomega.1c05557 |
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author | Xu, Han Tan, Yu Hou, Ziting Fu, Caiye Lin, Li-Rong |
author_facet | Xu, Han Tan, Yu Hou, Ziting Fu, Caiye Lin, Li-Rong |
author_sort | Xu, Han |
collection | PubMed |
description | [Image: see text] Five lanthanide complexes constructed from a stilbene derivative, (E)-N′,N′-bis(pyridin-2-ylmethyl)-4-styrylbenzoyl hydrazide (HL), and two β-diketonates (2-thenoyltrifluoroacetonate, tta), with or without a trifluoroacetate anion (CF(3)CO(2)(–)), namely, [Ln(tta)(2)(HL) (CF(3)CO(2))] [LnC(45)H(32)F(9)N(4)O(7)S(2), Ln = La (1), Nd (2), Eu (3), or Gd (4)] and [Yb(tta)(2)(L)] (YbC(43)H(31)F(6)N(4)O(5)S(2) (5), L = deprotonated HL), were synthesized and characterized. Crystals of these five complexes were obtained and analyzed by single-crystal X-ray diffraction. These complexes all belonged to the monoclinic P2(1)/c space group. For La(3+), Nd(3+), Eu(3+), and Gd(3+), the central lanthanide ion was nine-coordinate with a monocapped twisted square antiprism polyhedron geometry. The central Yb(3+) ion of complex 5 was eight-coordinate with a distorted double-capped triangular prism polyhedron geometry. Among the five complexes, trans-to-cis photoisomerization of the stilbene group in gadolinium complex 4 showed the largest quantum yield. Complexes 2, 3, and 4 showed dual luminescence and photoisomerization functions. The luminescence change of complex 3 was reversible upon the trans-to-cis photoisomerization process. The sensitization efficiencies of luminescent europium complex 3 in acetonitrile solutions and in the solid state were 49.9 and 42.6%, respectively. These medium sensitization efficiencies led to the observation of simultaneous photoisomerization and luminescence, which further confirmed our previous report that photoisomerization of the stilbene group within complexes was related to the lanthanide ion energy level and whether a ligand-to-metal center or ligand-to-ligand charge-transfer process was present. In complexes 1–5, in addition to the intramolecular absorption transition of the ligand itself (IL, π(HL)–π(HL)(*) and π(tta)–π(tta)*), the presence of a ligand-to-ligand charge-transfer transition between tta and HL (LLCT, π(tta)–π(HL)(*) or π(HL)–π(tta)(*)) indicated whether the triplet-state energy of HL was able to transfer to the excited energy level of the lanthanide ions, leading to different extents of HL photoisomerization. These results provide an important route for the design of new dual-function lanthanide-based optical switching materials. |
format | Online Article Text |
id | pubmed-8757447 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-87574472022-01-14 Insights into the Effect of Trans-to-Cis Photoisomerization of a Co-coordinated Stilbene Derivative on the Luminescence of Di-β-diketonate Lanthanide Complexes Xu, Han Tan, Yu Hou, Ziting Fu, Caiye Lin, Li-Rong ACS Omega [Image: see text] Five lanthanide complexes constructed from a stilbene derivative, (E)-N′,N′-bis(pyridin-2-ylmethyl)-4-styrylbenzoyl hydrazide (HL), and two β-diketonates (2-thenoyltrifluoroacetonate, tta), with or without a trifluoroacetate anion (CF(3)CO(2)(–)), namely, [Ln(tta)(2)(HL) (CF(3)CO(2))] [LnC(45)H(32)F(9)N(4)O(7)S(2), Ln = La (1), Nd (2), Eu (3), or Gd (4)] and [Yb(tta)(2)(L)] (YbC(43)H(31)F(6)N(4)O(5)S(2) (5), L = deprotonated HL), were synthesized and characterized. Crystals of these five complexes were obtained and analyzed by single-crystal X-ray diffraction. These complexes all belonged to the monoclinic P2(1)/c space group. For La(3+), Nd(3+), Eu(3+), and Gd(3+), the central lanthanide ion was nine-coordinate with a monocapped twisted square antiprism polyhedron geometry. The central Yb(3+) ion of complex 5 was eight-coordinate with a distorted double-capped triangular prism polyhedron geometry. Among the five complexes, trans-to-cis photoisomerization of the stilbene group in gadolinium complex 4 showed the largest quantum yield. Complexes 2, 3, and 4 showed dual luminescence and photoisomerization functions. The luminescence change of complex 3 was reversible upon the trans-to-cis photoisomerization process. The sensitization efficiencies of luminescent europium complex 3 in acetonitrile solutions and in the solid state were 49.9 and 42.6%, respectively. These medium sensitization efficiencies led to the observation of simultaneous photoisomerization and luminescence, which further confirmed our previous report that photoisomerization of the stilbene group within complexes was related to the lanthanide ion energy level and whether a ligand-to-metal center or ligand-to-ligand charge-transfer process was present. In complexes 1–5, in addition to the intramolecular absorption transition of the ligand itself (IL, π(HL)–π(HL)(*) and π(tta)–π(tta)*), the presence of a ligand-to-ligand charge-transfer transition between tta and HL (LLCT, π(tta)–π(HL)(*) or π(HL)–π(tta)(*)) indicated whether the triplet-state energy of HL was able to transfer to the excited energy level of the lanthanide ions, leading to different extents of HL photoisomerization. These results provide an important route for the design of new dual-function lanthanide-based optical switching materials. American Chemical Society 2021-12-17 /pmc/articles/PMC8757447/ /pubmed/35036758 http://dx.doi.org/10.1021/acsomega.1c05557 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/). |
spellingShingle | Xu, Han Tan, Yu Hou, Ziting Fu, Caiye Lin, Li-Rong Insights into the Effect of Trans-to-Cis Photoisomerization of a Co-coordinated Stilbene Derivative on the Luminescence of Di-β-diketonate Lanthanide Complexes |
title | Insights into the Effect of Trans-to-Cis Photoisomerization
of a Co-coordinated Stilbene Derivative on the Luminescence of Di-β-diketonate
Lanthanide Complexes |
title_full | Insights into the Effect of Trans-to-Cis Photoisomerization
of a Co-coordinated Stilbene Derivative on the Luminescence of Di-β-diketonate
Lanthanide Complexes |
title_fullStr | Insights into the Effect of Trans-to-Cis Photoisomerization
of a Co-coordinated Stilbene Derivative on the Luminescence of Di-β-diketonate
Lanthanide Complexes |
title_full_unstemmed | Insights into the Effect of Trans-to-Cis Photoisomerization
of a Co-coordinated Stilbene Derivative on the Luminescence of Di-β-diketonate
Lanthanide Complexes |
title_short | Insights into the Effect of Trans-to-Cis Photoisomerization
of a Co-coordinated Stilbene Derivative on the Luminescence of Di-β-diketonate
Lanthanide Complexes |
title_sort | insights into the effect of trans-to-cis photoisomerization
of a co-coordinated stilbene derivative on the luminescence of di-β-diketonate
lanthanide complexes |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8757447/ https://www.ncbi.nlm.nih.gov/pubmed/35036758 http://dx.doi.org/10.1021/acsomega.1c05557 |
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