Sensitised LnIII emission and excited-state dynamics of cofacial 'Pacman' porphyrin terpyridine complexes

Liew, Jane Y., Brown, Joshua J., Moore, Evan G. and Schwalbe, Matthias (2016) Sensitised LnIII emission and excited-state dynamics of cofacial 'Pacman' porphyrin terpyridine complexes. Chemistry, 22 45: 16178-16186. doi:10.1002/chem.201602189


Author Liew, Jane Y.
Brown, Joshua J.
Moore, Evan G.
Schwalbe, Matthias
Title Sensitised LnIII emission and excited-state dynamics of cofacial 'Pacman' porphyrin terpyridine complexes
Formatted title
Sensitised LnIII emission and excited-state dynamics of cofacial 'Pacman' porphyrin terpyridine complexes
Journal name Chemistry   Check publisher's open access policy
ISSN 1521-3765
0947-6539
Publication date 2016-01-01
Year available 2016
Sub-type Article (original research)
DOI 10.1002/chem.201602189
Open Access Status Not yet assessed
Volume 22
Issue 45
Start page 16178
End page 16186
Total pages 1
Place of publication Weinheim, Germany
Publisher Wiley
Language eng
Abstract An asymmetric 'Pacman' metalloligand, [Zn(PXT)], which features a cofacial ZnII -porphyrin unit (P) covalently attached to a terpyridine (T) chelating group via a rigid xanthene (X) moiety has been prepared, and its interactions with several different trivalent LnIII cations (NdIII , GdIII , YbIII and LuIII ) have been examined. The formation of 1:1 metal-ligand complexes was monitored by 1 H NMR spectroscopy and corroborated by HRMS data. Solution-stability constants were determined by UV/Vis titration, and the resulting complexes with NdIII or YbIII demonstrated sensitised emission in the NIR region due to energy transfer from the ZnII -porphyrin donor to LnIII acceptor. The energy transfer was investigated by transient absorption techniques, which provided insight into the kinetics and efficiency of the antenna effect.
Formatted abstract
An asymmetric ‘Pacman’ metalloligand, [Zn(PXT)], which features a cofacial ZnII–porphyrin unit (P) covalently attached to a terpyridine (T) chelating group via a rigid xanthene (X) moiety has been prepared, and its interactions with several different trivalent LnIII cations (NdIII, GdIII, YbIII and LuIII) have been examined. The formation of 1:1 metal–ligand complexes was monitored by 1H NMR spectroscopy and corroborated by HRMS data. Solution-stability constants were determined by UV/Vis titration, and the resulting complexes with NdIII or YbIII demonstrated sensitised emission in the NIR region due to energy transfer from the ZnII–porphyrin donor to LnIII acceptor. The energy transfer was investigated by transient absorption techniques, which provided insight into the kinetics and efficiency of the antenna effect.
Keyword Energy transfer
Lanthanides
Terpyridines
Transient absorption
Zinc porphyrins
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: HERDC Pre-Audit
School of Chemistry and Molecular Biosciences
 
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Created: Fri, 07 Oct 2016, 20:49:41 EST by Mrs Louise Nimwegen on behalf of School of Chemistry & Molecular Biosciences