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For a long time, the properties of transition metal and rare earth
compounds have fascinated chemists and physicists from a scientific
view-point, and more recently also their enormous potential as new
materials has been explored. Applications in different fields have
already been realized or are under c- rent investigation, for
example, new laser materials, IR to visible upconversion systems,
compounds for photolithographic processes, systems involving pho-
redox processes for solar energy conversion, new photovoltaic
devices, chemical sensors, biosensors, electroluminescent devices
(OLEDs) for flat panel display systems, supramolecular devices with
wide-range definable photophysical properties, materials for energy
harvesting, optical information and storage systems, etc. Metal
complexes are also highly important in biology and me- cine. Most
of the applications mentioned are directly related to the
properties of the electronic ground state and the lower-lying
excited states. Metal complexes with organic ligands or
organometallic compounds exhibit outstanding features as compared
to purely organic molecules. For instance, metal compounds can
often be prepared and applied in different oxidation states.
Furthermore, various types of low-lying electronic excitations can
be induced by a suitable choice of ligands, for example, such as
metal-centered transitions (MC, e. g. d-d* tran- tion),
ligand-centered (LC, e. g. n-n*), metal-to-ligand-charge transfer
(MLCT, e. g. d-7r*), intra-ligand-charge-transfer (ILCT)
transitions, etc. In particular, the orbitals involved in the
resulting lowest excited states determine the photoph- ical and
photochemical properties and thus the specific use of the compoun
There exists a large literature on the spectroscopic properties of
copper(II) com- 9 pounds. This is due to the simplicity of the d
electron configuration, the wide variety of stereochemistries that
copper(II) compounds can adopt, and the f- xional geometric
behavior that they sometimes exhibit [1]. The electronic and
geometric properties of a molecule are inexorably linked and this
is especially true with six-coordinate copper(II) compounds which
are subject to a Jahn-T- ler effect.However,the spectral-structural
correlations that are sometimes d- wn must often be viewed with
caution as the information contained in a typical solution UV-Vis
absorption spectrum of a copper(II) compound is limited. Meaningful
spectral-structural correlations can be obtained in a related
series of compounds where detailed spectroscopic data is available.
In the fol- 4- lowing sections two such series are examined; the
six-coordinate CuF and 6 2+ Cu(H O) ions doped as impurities in
single crystal hosts.Using low tempera- 2 6 ture polarized optical
spectroscopy and electron paramagnetic resonance, a very detailed
picture can be drawn about the geometry of these ions in both their
ground and excited electronic states. We then compare the
spectrosco- cally determined structural data with that obtained
from X-ray diffraction or EXAFS measurements.
The unique properties and applications of transition metal
compounds have long fascinated both physicists and chemists. This
volume presents theoretical and experimental studies for a deeper
understanding of the electronic and vibronic properties of these
compounds. In particular, an introduction into properties of spin
sublevels of dd*, dA*, and AA* states is given, and a modern ligand
field theory based on the Angular Overlap Model is presented. In
experimental case studies it is shown how to characterize different
types of electronic transitions using modern methods of laser
spectroscopy. Consequences of spin-orbit coupling, zero-field
splittings, spin-lattice relaxations, chromophore-matrix
interactions, Herzberg-Teller/Franck-Condon activities, and
localization/delocalization properties are treated.
Contents G. Blasse, "Vibrational Structure in the" "Luminescence
Spectra of Ions in Solids."-
A. Ceulemans, "The Doublet States in Chromium(III) Complexes." "A
Shell-Theoretic View."-
H.-H. Schmidtke, "Vibrational Progressions in Electronic" "Spectra
of Complex Compounds Indicating Strong Vibronic" "Coupling."-
P.E. Hoggard, "Sharp-Line Electronic Spectra and Metal-Ligand"
"Geometry."- M. Colombo, A. Hauser, H.U. Gudel, "Competition"
"Between Ligand Centered and Charge Transfer Lowest Excited"
"States in bis Cyclometalated Rh3+ and Ir3+ Complexes."- D. Wexler,
J.I. Zink, C. Reber, "Spectroscopic Manifestations of" "Potential"
"Surface Coupling Along Normal Coordinates in " "Transition" "
Metal Complexes.""
For a long time, the properties of transition metal and rare earth
compounds have fascinated chemists and physicists from a scientific
view-point, and more recently also their enormous potential as new
materials has been explored. Applications in different fields have
already been realized or are under c- rent investigation, for
example, new laser materials, IR to visible upconversion systems,
compounds for photolithographic processes, systems involving pho-
redox processes for solar energy conversion, new photovoltaic
devices, chemical sensors, biosensors, electroluminescent devices
(OLEDs) for flat panel display systems, supramolecular devices with
wide-range definable photophysical properties, materials for energy
harvesting, optical information and storage systems, etc. Metal
complexes are also highly important in biology and me- cine. Most
of the applications mentioned are directly related to the
properties of the electronic ground state and the lower-lying
excited states. Metal complexes with organic ligands or
organometallic compounds exhibit outstanding features as compared
to purely organic molecules. For instance, metal compounds can
often be prepared and applied in different oxidation states.
Furthermore, various types of low-lying electronic excitations can
be induced by a suitable choice of ligands, for example, such as
metal-centered transitions (MC, e. g. d-d* tran- tion),
ligand-centered (LC, e. g. n-n*), metal-to-ligand-charge transfer
(MLCT, e. g. d-7r*), intra-ligand-charge-transfer (ILCT)
transitions, etc. In particular, the orbitals involved in the
resulting lowest excited states determine the photoph- ical and
photochemical properties and thus the specific use of the compoun
There exists a large literature on the spectroscopic properties of
copper(II) com- 9 pounds. This is due to the simplicity of the d
electron configuration, the wide variety of stereochemistries that
copper(II) compounds can adopt, and the f- xional geometric
behavior that they sometimes exhibit [1]. The electronic and
geometric properties of a molecule are inexorably linked and this
is especially true with six-coordinate copper(II) compounds which
are subject to a Jahn-T- ler effect.However,the spectral-structural
correlations that are sometimes d- wn must often be viewed with
caution as the information contained in a typical solution UV-Vis
absorption spectrum of a copper(II) compound is limited. Meaningful
spectral-structural correlations can be obtained in a related
series of compounds where detailed spectroscopic data is available.
In the fol- 4- lowing sections two such series are examined; the
six-coordinate CuF and 6 2+ Cu(H O) ions doped as impurities in
single crystal hosts.Using low tempera- 2 6 ture polarized optical
spectroscopy and electron paramagnetic resonance, a very detailed
picture can be drawn about the geometry of these ions in both their
ground and excited electronic states. We then compare the
spectrosco- cally determined structural data with that obtained
from X-ray diffraction or EXAFS measurements.
The unique properties and applications of transition metal
compounds have long fascinated both physicists and chemists. This
volume presents theoretical and experimental studies for a deeper
understanding of the electronic and vibronic properties of these
compounds. In particular, an introduction into properties of spin
sublevels of dd*, dA*, and AA* states is given, and a modern ligand
field theory based on the Angular Overlap Model is presented. In
experimental case studies it is shown how to characterize different
types of electronic transitions using modern methods of laser
spectroscopy. Consequences of spin-orbit coupling, zero-field
splittings, spin-lattice relaxations, chromophore-matrix
interactions, Herzberg-Teller/Franck-Condon activities, and
localization/delocalization properties are treated.
The "Seventh International Symposium on the Photochemistry and
Photo- physics of Coordination Compounds" was held in the charming
Schlo~ Elmau lying in a hidden valley of the Bavarian Alps above
Garmisch- Partenkirchen, Federal Republic of Germany, from March 29
to April 2, 1987. About ninety participants from seventeen
countries including about thirty non-European scientists as far
away as Japan and Australia came together for this symposium.
Forty-five oral and twenty-five poster contributions were
presented. These presentations and the opportunity for many formal
and informal discussions stimulated an intense scienti- fic
interaction between the participants. This meeting followed
previous symposia held in Muhlheim 1974 (Koerner von Gustorf),
Ferrara 1976 (Carassiti, Scandola), Koln 1978 (Wasgestian),
Montreal 1980 (Serpone), Paris 1982 (Gianotti) and London 1984
(Harriman). The main fields covered by this 7th Symposium were
photo-redox processes, organometallic photochemistry, and
properties of metal centered excited states. Furthermore, special
complexes such as 2+ [Ru(bpy)3] and related compounds as well as
Cr(III)-complexes were discussed extensively. Moreover, a series of
potential applications such as solar energy conversion and storage
(e.g. water splitting) and photoresist technology were important
subjects of this meeting. Thus, it was shown again that the rapidly
expanding field of excited-state chemistry and physics of
coordination compounds has become an important part of inorganic
chemistry.
This brand-new monograph on organic light emitting diodes, edited
by a pioneer, and written by front-line researchers from academia
and industry, provides access to the latest findings in this
rapidly growing field. More than ten contributions cover all areas
-- from theory and basic principles, to different emitter materials
and applications in production.
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