Supramolecular Chemistry
141
pulsed Nd-YAG laser (10 Hz), or using an Edinburgh
Instruments mF microsecond flash lamp (1–1000 Hz)
as excitation source. Lifetime data were recorded using
the multi-channel scaling single-photon counting
method. Detector saturation was avoided in all circum-
stances by using minimal signal rate intensities combined
with extended data collection times. Lifetime data were
fitted to exponential decays using the tail fit option in
Edinburgh Instruments F900 PC software. UV–Vis
absorption spectra were recorded using either a Varian
Cary 50 single beam spectrometer or a Varian Cary 5000
dual beam spectrometer.
12.5 mmol dm23. Macrocycles were characterised by
positive-mode electrospray mass spectrometry and
steady-state
spectroscopy.
and
time-resolved
luminescence
Acknowledgements
We wish to thank the European Community Action Scheme
for the Mobility of University Students (ERASMUS), and
COST action D38 ‘Metal-Based Systems for Molecular
Imaging Applications’ and EPSRC for funding. Some of the
spectrometers used in this research were obtained, through
Birmingham Science City: Innovative Uses for Advanced
Materials in the Modern World (West Midlands Centre for
Advanced Materials Project 2), with support from Advantage
West Midlands (AWM) and part funded by the European
Regional Development Fund (ERDF).
4.2 N,N00-bis( p-thiophenolamide)diethylenetriamine-
N,N0,N00-triacetic acid, H3Lx
The synthetic route of this compound has been fully
described previously by Pikramenou and co-workers (18).
All characterisation data were consistent with that
previously reported: 1H NMR (300 MHz, d4-MeOH),
d ppm: 7.40 (4H, d); 7.13 (4H, d); 4.12 (2H, s); 3.62 (4H,
s); 3.59 (4H, s); 3.49 (4H, t); 3.22 (4H, t). MS (ES-TOFþ):
m/z 608 [M þ H]þ, 630 [M þ Na]þ. UV–Vis (MeOH):
lmax in nm (log 1) 264 (4.4).
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1
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4.3.1 Formation of dinuclear heterometallic
macrocycles: M1 and M2
Stock solutions (1 mM) of H3Lx, H3Ly, LnCl3.6H2O
and Ln0Cl3.6H2O in methanol or methanol-d were
initially prepared (M1: Ln ¼ Eu3þ, Ln0 ¼ Gd3þ; M2:
Ln ¼ Nd3þ, Ln0 ¼ Eu3þ). The stock solutions were then
used to form LnLx and Ln0Ly species directly in solution
(1:1 molar ratio of ligand to lanthanide) at a concentration
of 25 mmol dm23 by simple mixing and dilution in
methanol or methanol-d. Equal volumes of the solutions
of LnLx and Ln0Ly were then combined rapidly with
vigorous stirring and macrocycle formation was mon-
itored by UV–Vis absorption spectroscopy over 1 h. The
concentration of the macrocyclic species after mixing is