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http://hdl.handle.net/10773/35929
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DC Field | Value | Language |
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dc.contributor.author | Salerno, E. V. | pt_PT |
dc.contributor.author | Carneiro Neto, A. N. | pt_PT |
dc.contributor.author | Eliseeva, S. V. | pt_PT |
dc.contributor.author | Hernández-Rodríguez, M. A. | pt_PT |
dc.contributor.author | Lutter, J. C. | pt_PT |
dc.contributor.author | Lathion, T. | pt_PT |
dc.contributor.author | Kampf, J. W. | pt_PT |
dc.contributor.author | Petoud, S. | pt_PT |
dc.contributor.author | Carlos, Luís D. | pt_PT |
dc.contributor.author | Pecoraro, V. L. | pt_PT |
dc.date.accessioned | 2023-01-20T12:49:22Z | - |
dc.date.available | 2023-01-20T12:49:22Z | - |
dc.date.issued | 2022-11-12 | - |
dc.identifier.issn | 0002-7863 | pt_PT |
dc.identifier.uri | http://hdl.handle.net/10773/35929 | - |
dc.description.abstract | The effect of ligands' energy levels on thermal dependence of lanthanide emission was examined to create new molecular nanothermometers. A series of Ln2Ga8L8′L8″metallacrowns (shorthand Ln2L8′), where Ln = Gd3+, Tb3+, or Sm3+(H3L′ = salicylhydroxamic acid (H3shi), 5-methylsalicylhydroxamic acid (H3mshi), 5-methoxysalicylhydroxamic acid (H3moshi), and 3-hydroxy-2-naphthohydroxamic acid (H3nha)) and H2L″ = isophthalic acid (H2iph), was synthesized and characterized. Within the series, ligand-centered singlet state (S1) energy levels ranged from 23,300 to 27,800 cm-1, while triplet (T1) energy levels ranged from 18,150 to 21,980 cm-1. We demonstrated that the difference between T1levels and relevant energies of the excited 4G5/2level of Sm3+(17,800 cm-1) and 5D4level of Tb3+(20,400 cm-1) is the major parameter controlling thermal dependence of the emission intensity via the back energy transfer mechanism. However, when the energy difference between S1and T1levels is small (below 3760 cm-1), the S1→ T1intersystem crossing (and its reverse, S1→ T1) mechanism contributes to the thermal behavior of metallacrowns. Both mechanisms affect Ln3+-centered room-temperature quantum yields with values ranging from 2.07(6)% to 31.2(2)% for Tb2L8′and from 0.0267(7)% to 2.27(5)% for Sm2L8′. The maximal thermal dependence varies over a wide thermal range (ca. 150-350 K) based on energy gaps between relevant ligand-based and lanthanide-based electronic states. By mixing Tb2moshi8′with Sm2moshi8′in a 1:1 ratio, an optical thermometer with a relative thermal sensitivity larger than 3%/K at 225 K was created. Other temperature ranges are also accessible with this approach | pt_PT |
dc.language.iso | eng | pt_PT |
dc.publisher | American Chemical Society | pt_PT |
dc.relation | info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F50011%2F2020/PT | pt_PT |
dc.relation | info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDP%2F50011%2F2020/PT | pt_PT |
dc.relation | LA/P/0006/ 2020 | pt_PT |
dc.relation | info:eu-repo/grantAgreement/FCT/3599-PPCDT/PTDC%2FNAN-PRO%2F3881%2F2020/PT | pt_PT |
dc.rights | restrictedAccess | pt_PT |
dc.title | Tunable Optical Molecular Thermometers Based on Metallacrowns | pt_PT |
dc.type | article | pt_PT |
dc.description.version | published | pt_PT |
dc.peerreviewed | yes | pt_PT |
degois.publication.issue | 40 | pt_PT |
degois.publication.title | Journal of the American Chemical Society | pt_PT |
degois.publication.volume | 144 | pt_PT |
dc.identifier.doi | 10.1021/jacs.2c04821 | pt_PT |
dc.identifier.essn | 1520-5126 | pt_PT |
Appears in Collections: | CICECO - Artigos DFis - Artigos |
Files in This Item:
File | Description | Size | Format | |
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jacs.2c04821.pdf | 4.37 MB | Adobe PDF |
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