Lanthanide complexes electronic spectra

Hunt s group (50, 51) have pioneered the application of the Cl source to organometallics such as the iron tricarbonyl complex of heptafulvene, whose electron impact spectrum shows (M—CO)+ as the heaviest ion, in contrast to the methane Cl spectrum with the ion as base peak. Boron hydrides (52) and borazine (53) have also been studied. The methane Cl spectrum of arenechromium and -molybdenum (54) show protonation at the metal giving a protonated parent or molecular ion. Risby et al. have studied the isobutane Cl mass spectra of lanthanide 2,2,6,6-tetramethylheptane-3,5-dionates[Ln(thd)3] (55) and 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-oetanedione [H(fod)] lanthanide complexes (56). These latter complexes have been suggested as a means of analysis for the lanthanide elements. 

Figure 136 EL spectra of various organic LEDs employing lanthanide complexes as emitters, (a) ITO/TAD (triphenyldiamine derivative)/Eu(TTA)3(phen)(phen l,10-phenanthroline + 4,7-diphenyl-l,10-phenanthroline)/Alq3/MgAg (according to Ref. 425) (b) ITO/Eu (TTA)3 PBD/PBD/LiF/Mg, at the different voltages (after Ref. 539) (c) ITO/TPD/Tb (acac)3/Al, transitions of 4f electrons of the terbium Tb3+ ion are indicated on the sharp peak positions of this spectrum (after Ref. 19).

Deuterium quadrupole coupling constants can also be obtained from electron nuclear double resonance (ENDOR).19 30 An observation of the hyperfine structure caused by quadrupole coupling in the electron paramagnetic resonance (EPR) spectrum, as for many lanthanide complexes, has not been reported for deuterium. The determination of nuclear quadrupole coupling constants from Mossbauer spectroscopy is not applicable to the deuterium nucleus. 

Figure 2c shows the near-infrared luminescence spectrum of [Gd(hfac)3NIT-BzImH] compared to its lowest-energy absorption band system. At 5 K, both spectra show well-resolved structure that is similar to the patterns observed for the uncoordinated radical, as summarized in Tables 1 and 2. The corresponding electronic transitions can be observed for many other complexes of lanthanide or d-block metal ions with radical ligands [24-27, 30]. In general, the spectra for lanthanide complexes are very similar to those of the uncoordinated radicals. 

These lanthanide complexes produce spectral simplifications in the NMR spectrum of any compound with a relatively basic pair of electrons (an unshared pair) which can coordinate with Eu ". Typically, aldehydes, ketones, alcohols, thiols, ethers, and amines all interact ... 

Due to the modifications of the electronic cloud induced by complexation, the quantum yield and the excitation spectrum are also modified. As the direct determination of the absolute quantum yield is very difficult to achieve, one usually finds in the literature quantum yield values determined by comparison to well-known standards, such as quinine sulfate. For example, some values can be found in Georges (1993) or in Klink et al. (2000) for some europium complexes but may be found also in many other papers on lanthanide luminescence. Studies on the correlations between the photophysical properties of a given type of europium complexes and the energy levels can be found in Latva et al. (1997), Klink et al. (2000). A correlation has been found between the excitation properties and the stoichiometry of various Eu(III) complexes (Choppin and Wang, 1997). Note that the changes in the excitation maximum induced by complexation usually amount to a few tenths of nanometers, which requires high resolution for detection. In the case of Eu(III), a correlation has been found between the frequency... 

In lanthanide elements, the 5s and 5p shells are on the outside of the 4f shell. The 5s and 5p electrons are shielded, any force field (the crystal field or coordinating field in crystals or complexes) of the surrounding elements in complexes have little effect on the electrons in the 4f shell of the lanthanide elements. Therefore, the absorption spectra of lanthanide compounds are line-like spectra similar to those of free ions. This is different from the absorption spectra of d-block compounds. In d-block compounds, spectra originate from 3d 3d transitions. The nd shell is on the outside of the atoms so no shielding effect exists. Therefore, the 3d electrons are easily affected by crystal or coordinating fields. As a result, d-block elements show different absorption spectra in different compounds. Because of a shift in the spectrum line in the d-block, absorption spectra change from line spectra in free ions to band spectra in compounds. 

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