Dual visible and near-infrared luminescence in mononuclear macrocyclic erbium() complexes ligand and metal centred excitation
Considering the structural design of some of the scarce molecular-based Er-centred emitters in the literature, we explored the optical properties of three Er III hexaazamacrocyclic complexes, namely Er-EDA ( 1 ), Er-OPDA( 2 ) and Er-DAP( 3 ). The macrocyclic ligands in these complexes differ in the...
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Published in | Dalton transactions : an international journal of inorganic chemistry Vol. 52; no. 1; pp. 3158 - 3168 |
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Main Authors | , , , , , , , |
Format | Journal Article |
Published |
07.03.2023
|
Online Access | Get full text |
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Summary: | Considering the structural design of some of the scarce molecular-based Er-centred emitters in the literature, we explored the optical properties of three Er
III
hexaazamacrocyclic complexes, namely Er-EDA (
1
), Er-OPDA(
2
) and Er-DAP(
3
). The macrocyclic ligands in these complexes differ in the lateral spacers, and are derived from 2,6-pyridine-dicarbaldehyde and ethylenediamine (EDA),
ortho
-phenylenediamine (OPDA) or 1,3-diaminopropane (DAP). Upon ligand-centred excitation, the bluish-green and green emissions of the Er
III
ion were detected only for the complexes containing macrocycles with aliphatic spacers (
1
and
3
), which evidenced that these ligands can sensitize the Er
III
luminescence. On the other hand, the ligand derived from the aromatic diamine (
2
) does not sensitize the Er
III
luminescence. Energy transfer mechanisms, temperature sensing, CIE coordinates and CCT values were analyzed. Besides the excitation in the ligands, the erbium-centred excitation at 980 nm allowed the detection, in all cases, of bluish-green, green and red up-converted emissions, and also the downshifted NIR emission. The possible mechanisms involved in these transitions were described and analyzed according to the available data.
The optical studies of three macrocyclic Er
III
complexes showed visible upconversion and NIR-downshifted emission upon metal centred excitation. Besides, macrocyclic ligands with aliphatic spacers act as antennas to sensitize the Er
III
luminescence. |
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Bibliography: | https://doi.org/10.1039/d2dt03447f Electronic supplementary information (ESI) available: Diffuse reflectance, NIR emission, phosphorescence and up-conversion and downshifting spectra of the complexes. See DOI |
ISSN: | 1477-9226 1477-9234 |
DOI: | 10.1039/d2dt03447f |