By Daniel R. Gamelin, Hans U. Gudel (auth.), Prof. Dr. Hartmut Yersin (eds.)
There exists a wide literature at the spectroscopic houses of copper(II) com- nine kilos. this is often as a result of simplicity of the d electron configuration, the big variety of stereochemistries that copper(II) compounds can undertake, and the f- xional geometric habit that they typically show [1]. The digital and geometric houses of a molecule are inexorably associated and this is often very true with six-coordinate copper(II) compounds that are topic to a Jahn-T- ler effect.However,the spectral-structural correlations which are occasionally d- wn needs to frequently be seen with warning because the details contained in a customary answer UV-Vis absorption spectrum of a copper(II) compound is proscribed. significant spectral-structural correlations could be got in a similar sequence of compounds the place precise spectroscopic facts is accessible. within the fol- four– lowing sections such sequence are tested; the six-coordinate CuF and six 2+ Cu(H O) ions doped as impurities in unmarried crystal hosts.Using low tempera- 2 6 ture polarized optical spectroscopy and electron paramagnetic resonance, a truly particular photo should be drawn concerning the geometry of those ions in either their floor and excited digital states. We then evaluate the spectrosco- cally decided structural information with that got from X-ray diffraction or EXAFS measurements.
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Extra info for Transition Metal and Rare Earth Compounds: Excited States, Transitions, Interactions II
Example text
5 K power-dependence data in Fig. 14a, b, increasing the excitation power from the low-power excitation limit results in a sharp jump in both VIS and NIR luminescence intensities at a certain critical power. Reversing the direction of the power sweep also results in a sharp jump on the return path, but this jump occurs at a lower power than the forward jump, resulting in a hysteresis behavior with a distinct region of bistability. Monitoring the transmission of the laser beam shows that the absorption of the sample also increases and decreases at these same critical powers (Fig.
The ratio of ETU intensities is therefore estimated to be IMo/IRe ª 10–5, despite a DA spectral overlap integral that is approximately three times larger in Mo3+ than in Re4+ due to the broadband nature of the acceptor (4T2) absorption feature. This is consistent with the experimental upper limit for one-color excitation of IMo/IRe £ 10–3. Introduction of a second color in Mo3+ excitation bypasses the spin restrictions of Eq. (9) by introducing direct 2E Æ 2T2 ESA, and renders the upconversion observable under these conditions.
Luminescence is observed from both the first (2T1/2E, NIR) and second (2T2, red) excited-state multiplets in both ions [69, 70]. In Mo3+, excitation into the higher-energy, broader, and more intense 4T2 and 4T1 interconfigurational d-d transitions leads to rapid relaxation followed by red 2T2 Æ 4A2 luminescence. 2T2 luminescence is observed in both ions with NIR excitation [68]. 5% Re4+ :Cs2ZrCl6 is shown in Fig. 19a. Fig. 18. 7, B = 487 [81]. Up arrows indicate two-photon excitation processes observed in Mo3+ and Re4+.