C. Piguet et al.
FULL PAPER
fiber with protection oil. Cell dimensions and intensities were measured at
200 K on a Stoe IPDS diffractometer with graphite-monochromated MoKa
radiation (l 0.7107 ä); 131723measured reflections, 2 qmax 51.98, 42677
unique reflections of wich 22616 were observed [jFo j> 4s(Fo)]; Rint for
89046 equivalent reflections 0.071. Data were corrected for Lorentz and
polarization effects and for absorption (min/max transmission 0.7552/
0.8963). The structure was solved by direct methods (SIR97);[61] all other
calculation were performed with XTAL system[62] and ORTEP[63] pro-
grams. Full-matrix least-squares refinement based on F using weight of 1/
(s2(Fo) 0.0001(Fo2) gave final values R 0.055, wR 0.055, and S
1.814(9) for 3024 variables and 24081 contributing reflections. The final
difference electron density map showed a maximum of 1.29 and a
minimum of À1.62 eäÀ3. The hydrogen atoms were placed in calculated
positions and contributed to Fc calculations. The methyl group C53a was
disordered and refined with two distinct atomic sites and population
parameters of 0.7/0.3. The anions were refined with isotropic displacement
parameters and restraints on bond distances and bond angles.
Acknowledgement
¬ ¡
We are grateful to Ms. Helene Lartigue, Mr. Laurent Gaudard and Mr.
Frederic Gumy for technical assistance. This work was supported through
grants from the Swiss National Science Foundation.
¬
¬
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Finnigan-4000 instruments. Pneumatically-assisted electrospray (ESI-MS)
mass spectra were recorded from 10À4 m acetonitrile solutions on API III
and API 3000 tandem mass spectrometers (AB/MDS Sciex) by infusion at
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4
10 mLminÀ1. The spectra were recorded under low up-front declustering
or collision induced dissociation (CID) conditions, typically DV 0 3 0 V
between the orifice and the first quadrupole of the spectrometer. The
experimental procedures for high-resolution, laser-excited luminescence
measurements have been published previously.[64] Solid-state samples were
finely powdered and low temperatures (295 10 K) were achieved by
means of a Cryodyne Model 22 closed-cycle refrigerator from CTI
Cryogenics. Luminescence spectra were corrected for the instrumental
function, but not excitation spectra. Lifetimes are averages of at least 3
5 independent determinations and were measured using excitation pro-
vided by a Quantum Brillant Nd:YAG laser equipped with frequency
doubler, tripler, and quadrupler as well as with an OPOTEK MagicPrismTM
OPO crystal. Ligand excitation and emission spectra, as well as quantum
yields were recorded on a Perkin Elmer LS-50B spectrometer equipped
for low-temperature measurements. The quantum yields F were calculated
by using the Equation (14), in which x refers to the sample and r to the
reference; A is the absorbance, nÄ the excitation wavenumber used, I the
intensity of the excitation light at this energy, n the refractive index and D
the integrated emitted intensity. [Eu(terpy)3](ClO4)3 (F 1.3%, acetoni-
trile, 10À3 m) and [Tb(terpy)3](ClO4)3 (F 4.7%, acetonitrile, 10À3 m) were
used as references for the determination of quantum yields of respectively
Eu- and Tb-containing samples.[33, 52] Elemental analyses were performed
by Dr. H. Eder from the microchemical Laboratory of the University of
Geneva.
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¬
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Williams, J. Alloys Compd. 1995, 225, 324.
Fx Arꢀn Irꢀn n2x Dx
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