Self-assembly of highly luminescent lanthanide complexes promoted by pyridine-tetrazolate ligands

Two tridentate pyridine-tetrazolate ligands (H(2)pytz and H(2)pytzc), analogues of the well-known dipicolinate (H(2)dpa) ligand, have been synthesized in a straightforward manner and used for lanthanide(III) coordination. The structures of the resulting tris-ligand complexes were determined in solut...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2012-01, Vol.41 (4), p.1268-1277
Main Authors: Andreiadis, Eugen S, Imbert, Daniel, Pécaut, Jacques, Demadrille, Renaud, Mazzanti, Marinella
Format: Article
Language:English
Subjects:
Absorption
Analytical chemistry
Chemical Sciences
Diffraction
Emission
Engineering Sciences
Lanthanides
Lanthanoid Series Elements - chemistry
Ligands
Luminescence
Luminescent Agents - chemical synthesis
Luminescent Agents - chemistry
Material chemistry
Models, Molecular
Molecular Conformation
Optics
Organic chemistry
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
Photonic
Pyridines - chemistry
Self assembly
Solid state
Solubility
Solutions
Tetrazoles - chemistry
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Summary:Two tridentate pyridine-tetrazolate ligands (H(2)pytz and H(2)pytzc), analogues of the well-known dipicolinate (H(2)dpa) ligand, have been synthesized in a straightforward manner and used for lanthanide(III) coordination. The structures of the resulting tris-ligand complexes were determined in solution ((1)H-NMR), where they remain undissociated, as well as in the solid state (X-ray diffraction). The solubility of these anionic complexes can be easily tuned by changing the countercation. The bis-tetrazolate-pyridine ligand H(2)pytz sensitizes very efficiently both the visible and near-IR emission of the lanthanides, with unusually high luminescence quantum yields in solid state (61% and 65% for Eu and Tb, respectively, and 0.21% for Nd) and in water (63% for Tb and 18% for Eu). Furthermore, the absorption window of the complexes is significantly extended towards the visible region up to 330 nm. The results show that the bis-tetrazolate-pyridine ligand provides a very attractive alternative to the classic dipicolinate ligand.
ISSN:1477-9226
1477-9234
DOI:10.1039/c1dt11627d