Issue 37, 2013
From the journal:

Dalton Transactions

Preparation and photophysical studies of [Ln(hfac)3DPEPO], Ln = Eu, Tb, Yb, Nd, Gd; interpretation of total photoluminescence quantum yields†‡

Martina Congiu,a   Mohamed Alamiry,a   Omar Moudam,a   Serena Ciorba,b   Patricia R. Richardson,a   Laurent Maron,c   Anita C. Jones,a   Bryce S. Richardsb  and  Neil Robertson*a  

* Corresponding authors

a School of Chemistry and EaStCHEM Research School, University of Edinburgh, West Mains Road, Edinburgh, UK
E-mail: neil.robertson@ed.ac.uk

b School of Engineering and Physical Science, Heriot-Watt University, Edinburgh, UK

c Laboratoire de Physique et Chimie de Nano-objets, Institut National des Sciences Appliquées, 135 avenue de Rangueil, Toulouse, Cedex 4, France

Abstract

Synthesis and photophysical characterisation of [Ln(hfac)3DPEPO] complexes (with Ln = Eu, Tb, Yb, Nd, Gd) has been carried out to investigate the factors responsible for the variation in total photoluminescence quantum yield within this family of emissive lanthanide complexes. Electronic absorption and emission spectroscopy, in conjunction with DFT calculations of the excited state of the Eu complex, elucidate the role of each ligand in the sensitisation of the lanthanide through the antenna effect. The X-ray crystal structure of [Gd(hfac)3DPEPO] has been determined and shows an 8-coordinate environment around the Gd and a ten-membered chelate ring involving the DPEPO ligand. Total photoluminescence quantum yields were measured to be 6%, 1% and 2% for Ln = Tb, Nd and Yb, respectively, in comparison with around 80% for Ln = Eu. The lower quantum yield for Nd and Yb, compared with Eu, can be attributed to more efficient quenching of the excited Ln state by high-energy oscillations within the ligands, whereas the lower quantum yield for Tb is assigned to a combination of poor energy transfer from the ligand excited state to the Tb and longer radiative lifetime.

Graphical abstract: Preparation and photophysical studies of [Ln(hfac)3DPEPO], Ln = Eu, Tb, Yb, Nd, Gd; interpretation of total photoluminescence quantum yields

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Article information

DOI
https://doi.org/10.1039/C3DT51380G
Article type
Paper
Submitted
27 May 2013
Accepted
19 Jul 2013
First published
30 Jul 2013

Dalton Trans., 2013,42, 13537-13545

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Preparation and photophysical studies of [Ln(hfac)3DPEPO], Ln = Eu, Tb, Yb, Nd, Gd; interpretation of total photoluminescence quantum yields

M. Congiu, M. Alamiry, O. Moudam, S. Ciorba, P. R. Richardson, L. Maron, A. C. Jones, B. S. Richards and N. Robertson, Dalton Trans., 2013, 42, 13537 DOI: 10.1039/C3DT51380G

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