Li, N, Subramanian, GS, Matthews, PD ORCID: 0000-0002-1362-8003, Xiao, J, Chellappan, V, Rosser, TE, Reisner, E, Luo, H-K and Wright, DS (2018) Energy transfer and photoluminescence properties of lanthanide-containing polyoxotitanate cages coordinated by salicylate ligands. Dalton Transactions, 47 (16). pp. 5679-5686. ISSN 1477-9234

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Abstract

Polyoxotitanate (POT) cages have attracted considerable attention recently; much of this from the fact that they can be considered to be structural models for the technologically important semiconductor TiO2. Among the reported POT cages, lanthanide-containing (Ln-POT) cages are of particular interest owing to the fascinating luminescence properties of Ln(3+) ions and the versatile coordination environments that they can adopt. In the present study, we report the energy transfer mechanism and photoluminescence properties of a series of isostructural Ln-POT cages coordinated by salicylate ligands, of general formula [LnTi(6)O(3)((OPr)-Pr-i)(9)(salicylate)(6)] (Ln-1, Ln = La to Er excluding Pm). Both visible (for Pr-1, Sm-1, Eu-1, Ho-1 and Er-1) and near-infrared (for Nd-1 and Er-1) Ln(3+)-centred photoluminescence can be sensitised in solution, and most importantly, their excitation bands all extend well into the visible region up to 475 nm. With the assistance of steady-state and time-resolved photoluminescence spectroscopy, an energy-transfer mechanism involving the salicylate-to-Ti4+ charge-transfer state is proposed to account for the largely red-shifted excitation wavelengths of these Ln-1 cages. The photoluminescence quantum yield of Nd-1 upon excitation via the charge-transfer state reaches 0.30 +/- 0.01% in solution, making it among the highest reported values for Nd3+-complexes in the literature.

Item Type: Article
Additional Information: This is the accepted author manuscript (AAM). The final published version (version of record) is available online via Royal Society of Chemistry at http://dx.doi.org/10.1039/c8dt00825f Please refer to any applicable terms of use of the publisher.
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Natural Sciences > School of Chemical and Physical Sciences
Depositing User: Symplectic
Date Deposited: 06 Apr 2018 10:03
Last Modified: 10 Aug 2018 10:56
URI: http://eprints.keele.ac.uk/id/eprint/4726

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