Circularly Polarized Luminescence from New Heteroleptic Eu(III) and Tb(III) Complexes
The complexes [Eu(bpcd)(tta)], [Eu(bpcd)(Coum)], and [Tb(bpcd)(Coum)] [tta = 2-thenoyltrifluoroacetyl-acetonate, Coum = 3-acetyl-4-hydroxy-coumarin, and bpcd = N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane-N,N'-diacetate] have been synthesized and characterized from photophysical and thermodynamic points of view. The optical and chiroptical properties of these complexes, such as the total luminescence, decay curves of the Ln(III) luminescence, electronic circular dichroism, and circularly polarized luminescence, have been investigated. Interestingly, the number of coordinated solvent (methanol) molecules is sensitive to the nature of the metal ion. This number, estimated by spectroscopy, is >1 for Eu(III)-based complexes and <1 for Tb(III)-based complexes. A possible explanation for this behavior is provided via the study of the minimum energy structure obtained by density functional theory (DFT) calculations on the model complexes of the diamagnetic Y(III) and La(III) counterparts [Y(bpcd)(tta)], [Y(bpcd)(Coum)], and [La(bpcd)(Coum)]. By time-dependent DFT calculations, estimation of donor-acceptor (D-A) distances and of the energy position of the S1 and T1 ligand excited states involved in the antenna effect was possible. These data are useful for rationalizing the different sensitization efficiencies (ηsens) of the antennae toward Eu(III) and Tb(III). The tta ligand is an optimal antenna for sensitizing Eu(III) luminescence, while the Coum ligand sensitizes better Tb(III) luminescence {ϕovl = 55%; ηsens ≥ 55% for the [Tb(bpcd)(Coum)] complex}. Finally, for the [Eu(bpcd)(tta)] complex, a sizable value of glum (0.26) and a good quantum yield (26%) were measured.
| Medienart: |
E-Artikel |
|---|
| Erscheinungsjahr: |
2023 |
|---|---|
| Erschienen: |
2023 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:62 |
|---|---|
| Enthalten in: |
Inorganic chemistry - 62(2023), 23 vom: 12. Juni, Seite 8812-8822 |
| Sprache: |
Englisch |
|---|
| Beteiligte Personen: |
Ruggieri, Silvia [VerfasserIn] |
|---|
| Links: |
|---|
| Themen: |
|---|
| Anmerkungen: |
Date Completed 12.06.2023 Date Revised 16.06.2023 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
|---|
| doi: |
10.1021/acs.inorgchem.3c00196 |
|---|
| funding: |
|
|---|---|
| Förderinstitution / Projekttitel: |
|
| PPN (Katalog-ID): |
NLM357644131 |
|---|
| LEADER | 01000naa a22002652 4500 | ||
|---|---|---|---|
| 001 | NLM357644131 | ||
| 003 | DE-627 | ||
| 005 | 20231226073036.0 | ||
| 007 | cr uuu---uuuuu | ||
| 008 | 231226s2023 xx |||||o 00| ||eng c | ||
| 024 | 7 | |a 10.1021/acs.inorgchem.3c00196 |2 doi | |
| 028 | 5 | 2 | |a pubmed24n1192.xml |
| 035 | |a (DE-627)NLM357644131 | ||
| 035 | |a (NLM)37262334 | ||
| 040 | |a DE-627 |b ger |c DE-627 |e rakwb | ||
| 041 | |a eng | ||
| 100 | 1 | |a Ruggieri, Silvia |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Circularly Polarized Luminescence from New Heteroleptic Eu(III) and Tb(III) Complexes |
| 264 | 1 | |c 2023 | |
| 336 | |a Text |b txt |2 rdacontent | ||
| 337 | |a ƒaComputermedien |b c |2 rdamedia | ||
| 338 | |a ƒa Online-Ressource |b cr |2 rdacarrier | ||
| 500 | |a Date Completed 12.06.2023 | ||
| 500 | |a Date Revised 16.06.2023 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a The complexes [Eu(bpcd)(tta)], [Eu(bpcd)(Coum)], and [Tb(bpcd)(Coum)] [tta = 2-thenoyltrifluoroacetyl-acetonate, Coum = 3-acetyl-4-hydroxy-coumarin, and bpcd = N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane-N,N'-diacetate] have been synthesized and characterized from photophysical and thermodynamic points of view. The optical and chiroptical properties of these complexes, such as the total luminescence, decay curves of the Ln(III) luminescence, electronic circular dichroism, and circularly polarized luminescence, have been investigated. Interestingly, the number of coordinated solvent (methanol) molecules is sensitive to the nature of the metal ion. This number, estimated by spectroscopy, is >1 for Eu(III)-based complexes and <1 for Tb(III)-based complexes. A possible explanation for this behavior is provided via the study of the minimum energy structure obtained by density functional theory (DFT) calculations on the model complexes of the diamagnetic Y(III) and La(III) counterparts [Y(bpcd)(tta)], [Y(bpcd)(Coum)], and [La(bpcd)(Coum)]. By time-dependent DFT calculations, estimation of donor-acceptor (D-A) distances and of the energy position of the S1 and T1 ligand excited states involved in the antenna effect was possible. These data are useful for rationalizing the different sensitization efficiencies (ηsens) of the antennae toward Eu(III) and Tb(III). The tta ligand is an optimal antenna for sensitizing Eu(III) luminescence, while the Coum ligand sensitizes better Tb(III) luminescence {ϕovl = 55%; ηsens ≥ 55% for the [Tb(bpcd)(Coum)] complex}. Finally, for the [Eu(bpcd)(tta)] complex, a sizable value of glum (0.26) and a good quantum yield (26%) were measured | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Mizzoni, Silvia |e verfasserin |4 aut | |
| 700 | 1 | |a Nardon, Chiara |e verfasserin |4 aut | |
| 700 | 1 | |a Cavalli, Enrico |e verfasserin |4 aut | |
| 700 | 1 | |a Sissa, Cristina |e verfasserin |4 aut | |
| 700 | 1 | |a Anselmi, Michele |e verfasserin |4 aut | |
| 700 | 1 | |a Cozzi, Pier Giorgio |e verfasserin |4 aut | |
| 700 | 1 | |a Gualandi, Andrea |e verfasserin |4 aut | |
| 700 | 1 | |a Sanadar, Martina |e verfasserin |4 aut | |
| 700 | 1 | |a Melchior, Andrea |e verfasserin |4 aut | |
| 700 | 1 | |a Zinna, Francesco |e verfasserin |4 aut | |
| 700 | 1 | |a Willis, Oliver G |e verfasserin |4 aut | |
| 700 | 1 | |a Di Bari, Lorenzo |e verfasserin |4 aut | |
| 700 | 1 | |a Piccinelli, Fabio |e verfasserin |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t Inorganic chemistry |d 1966 |g 62(2023), 23 vom: 12. Juni, Seite 8812-8822 |w (DE-627)NLM110650298 |x 1520-510X |7 nnns |
| 773 | 1 | 8 | |g volume:62 |g year:2023 |g number:23 |g day:12 |g month:06 |g pages:8812-8822 |
| 856 | 4 | 0 | |u http://dx.doi.org/10.1021/acs.inorgchem.3c00196 |3 Volltext |
| 912 | |a GBV_USEFLAG_A | ||
| 912 | |a GBV_NLM | ||
| 951 | |a AR | ||
| 952 | |d 62 |j 2023 |e 23 |b 12 |c 06 |h 8812-8822 | ||