Mixed Tb/Dy coordination ladders based on tetra(carboxymethyl)thiacalix[4]arene: a new avenue towards luminescent molecular nanomagnets
The macrocyclic ligand calix[4]arene ( L1 ) and its sulphur-containing analogue thia[4]calixarene ( L2 ) are promising precursors for functional molecular materials as they offer rational functionalization with various organic groups. Here, we present the first example of lanthanide-based coordinati...
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| Published in: | RSC advances Vol. 1; no. 2; pp. 11755 - 11765 |
|---|---|
| Main Authors: | , , , , , , , , , , , , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
England
Royal Society of Chemistry
24-03-2020
The Royal Society of Chemistry |
| Subjects: | |
| Online Access: | Get full text |
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| Summary: | The macrocyclic ligand calix[4]arene (
L1
) and its sulphur-containing analogue thia[4]calixarene (
L2
) are promising precursors for functional molecular materials as they offer rational functionalization with various organic groups. Here, we present the first example of lanthanide-based coordination polymers built from the macrocyclic thiacalix[4]arene backbone bearing four carboxylic moieties, namely, ligand
H
4
L3
. The combination of
H
4
L3
with the Tb
3+
and Dy
3+
cations led to the formation of 1D ladder-type coordination polymers with the formula [Ln
III
HL3
DMF
3
]·(DMF) (where DMF = dimethylformamide and Ln = Tb or Dy, denoted as
HL3-Tb
and
HL3-Dy
), which resulted from the coordination of the lanthanide cations with the partially deprotonated ligand
HL3
3−
that behaved as a T-shape connector. The coordination sphere around the metal was completed by the coordinated DMF solvent molecules. By combining both Tb
3+
and Dy
3+
cations, isostructural heterobimetallic solid solutions
HL3-Tb
1−
x
Dy
x
were also prepared.
HL3-Tb
and
HL3-Dy
showed visible light photoluminescence originating from the f-f electronic transitions of pale green emissive Tb
3+
and pale yellow emissive Dy
3+
with efficient sensitization by the functionalized thia[4]calixarene ligand
HL3
. In the
HL3-Tb
1−
x
Dy
x
solid solutions, the Tb/Dy ratio governed both the emission colour as well as the emission quantum yield, which reached even 28% at room temperature for
HL3-Tb
. Moreover,
HL3-Dy
exhibited a slow magnetic relaxation effect related to the magnetic anisotropy of the dodecahedral Dy
3+
complexes, which were well isolated in the crystal lattice by expanded organic spacers.
The single crystals of the two isostructural Tb
3+
- and Dy
3+
-based coordination polymers (
HL3-Tb
and
HL3-Dy
) were structurally characterized, and their photophysical properties were investigated, together with their corresponding solid solutions. |
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| Bibliography: | 10.1039/d0ra01263g 1898826 For ESI and crystallographic data in CIF or other electronic format see DOI Electronic supplementary information (ESI) available: Analysis using Shape program, measured cells for the solid solutions, EDS analysis for the solid solutions, excitation spectra, absolute luminescence quantum yields, decay profile analysis and details of magnetic measurements. CCDC 1898825 and ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 PMCID: PMC9050570 |
| ISSN: | 2046-2069 2046-2069 |
| DOI: | 10.1039/d0ra01263g |