Please use this identifier to cite or link to this item: http://hdl.handle.net/2381/44279
Title: Optical Properties of Heavily Fluorinated Lanthanide Tris beta-Diketonate Phosphine Oxide Adducts
Authors: Swinburne, AN
Paden, MHL
Chan, TL
Randall, S
Ortu, F
Kenwright, AM
Natrajan, LS
First Published: 20-Sep-2016
Publisher: MDPI
Citation: Inorganics, 2016, 4 (3), 27
Abstract: The construction of lanthanide(III) chelates that exhibit superior photophysical properties holds great importance in biological and materials science. One strategy to increase the luminescence properties of lanthanide(III) chelates is to hinder competitive non-radiative decay processes through perfluorination of the chelating ligands. Here, the synthesis of two families of heavily fluorinated lanthanide(III) β-diketonate complexes bearing monodentate perfluorinated tris phenyl phosphine oxide ligands have been prepared through a facile one pot reaction [Ln(hfac)3{(ArF)3PO}(H2O)] and [Ln(F7-acac)3{(ArF)3PO}2] (where Ln = Sm3+, Eu3+, Tb3+, Er3+ and Yb3+). Single crystal X-ray diffraction analysis in combination with photophysical studies have been performed to investigate the factors responsible for the differences in the luminescence lifetimes and intrinsic quantum yields of the complexes. Replacement of both bound H2O and C–H oscillators in the ligand backbone has a dramatic effect on the photophysical properties of the complexes, particularly for the near infra-red emitting ion Yb3+, where a five fold increase in luminescence lifetime and quantum yield is observed. The complexes [Sm(hfac)3{(ArF)3PO}(H2O)] (1), [Yb(hfac)3{(ArF)3PO}(H2O)] (5), [Sm(F7-acac)3{(ArF)3PO}2] (6) and [Yb(F7-acac)3{(ArF)3PO}2] (10) exhibit unusually long luminescence lifetimes and attractive intrinsic quantum yields of emission in fluid solution (ΦLn = 3.4% (1); 1.4% (10)) and in the solid state (ΦLn = 8.5% (1); 2.0% (5); 26% (6); 11% (10)), which are amongst the largest values for this class of compounds to date.
DOI Link: 10.3390/inorganics4030027
ISSN: 2304-6740
Links: https://www.mdpi.com/2304-6740/4/3/27
http://hdl.handle.net/2381/44279
Version: Publisher Version
Status: Peer-reviewed
Type: Journal Article
Rights: Copyright © the authors, 2016. This is an open-access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.
Description: The following are available online at www.mdpi.com/2304-6740/4/3/27/s1, Table S1: Single Crystal X-ray Data Collection and Structural Refinement for the Complexes and unit cell parameters for 5; Figures S1–S7: 19F and 31P{1H} NMR spectra for selected complexes (1, 3, 4, 5, 8, 9 and 10).
Appears in Collections:Published Articles, Dept. of Chemistry

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