Table Of ContentPhotochemistry and
Photophysics of
Coordination Compounds
Edited by
H. Yersin and A. Vogler
With 145 Figures and 38 Tables
Springer-Verlag
Berlin Heidelberg New York
London Paris Tokyo
Proceedings of the Seventh International Symposium
on the Photochemistry and Photophysics of Coordination Compounds
ElmauIFRG, March 29-April2, 1987
Priv.-Doz. Dr. Hartmut Yersin
Institut fUr Physikalische und Theoretische Chemie
Universitiit Regensburg
Universitiitsstr.31, 8400 Regensburg, FRG
Prof. Dr.Arnd Vogler
Institut fUr Anorganische Chemie, Universitiit Regensburg
8400 Regensburg, FRG
ISBN-13:978-3-540-17808-8 e-ISBN-13:978-3-642-72666-8
DOl: 10.1007/978-3-642-72666-8
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215213140-543210
PREFACE
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.
The organization of this symposium was made possible financially
through the generosity of Deutsche Forschungsgemeinschaft, Fonds der
Chemischen Industrie, BASF AG, Bayer AG, BMW AG, CIBA-GEIGY AG,
CYANAMID GMBH, Degussa AG, HOECHST AG, DR. SEITNER-Me~technik,
Siemens AG, and Wacker-Chemie GmbH.
Regensburg, July 1987
Arnd Vogler and Hartmut Yersin
TABLE OF CONTENTS
Topic 1: Metal-Centered Excited States
Polarized Luminescence of [Pt(CN)2bipy] Single Crystals - Magnetic
Field and Temperature Effects
(J. Biedermann, M. Wallfahrer, G. Gliemann) ••••.••.••••••••••.••••••• 3
Light-Induced Excited Spin State Trapping in Iron(II) Complexea
(S. Decurtins, P. GUtlich, A. Hauser, H. Spiering) •••..•••.••••••••• 9
Infrared Luminescence Spectroscopy of v3+ Doped CS2NaYX6 (X=Cl,Br)
(C. Reber, H.U. GUdel) ••••••••••••••••••.•••.••••.••••••••••.•••••• 17
Recent Progress in Uranyl Photo-Physics
(R. Reisfeld, C.K. J¢rgensen) ..••••.•.•••..••••••••.•••••.•.••••.•• 21
Effects of Macrocyclic and Cryptand Ligands on Photophysics of Eu3+
Ions
(N. Sabbatini, S. Perathoner, L. De Cola) ••••••••••.•••••.•••••••• 25
Topic 2: Photophysics and Photochemistry of Cr(III) Complexes
Ligand Field Analysis of the Doublet Excited States in Chromium(III)
Trischelated Complexes
(A. Ceulemans, N. Bongaerts, L.G. Vanquickenborne) •••••••.•••••.•.• 31
Quenching of Three Photoaquation Modes of a Chromium(III) Acidoammine~
(A. Damiani, P. Riccieri, E. Zinato) ••.••••.••••.•••••••••.••••••• 35
Stereochemical Constraints on the Excited State Behavior of Chro
mium(III)
(J.F. Endicott, C.K. Ryu, R.B. Lessard, P.E. Hoggard) ••.•••••.•••. 39
Excited State Behavior as a Probe of Ground-State Ion-Pair Interac
tions in Chromium(III)-Polypyridyl Complexes
(M.Z. Hoffman, N. Serpone) ••••••••••.••••••••••.•••.•••••••••••••• 43
Counter ion Effects on Doublet Splittings of Chromium(III) Complexes
(P.E. Hoggard, K.-W. Lee) ••••••••••••••••••••.•••••••••..•••••••.• 49
Spectrum-Structure Correlations in Hexacoordinated Transition Metal
Complexes
(T. Schonherr) ••••••••••••••••••.••••.•••••••••••.•.••..•••.••••• , 55
Multiphoton-Induced Picosecond Photophysics of Chromium(III)-Poly
pyridyl Complexes
(N. Serpone, M.Z. Hoffman) ••••••••••••••••••••••••.••••••.••••.••• 61
Topic_3: Excited State Properties of Tris-2,2'-Bipyridine Ruthenium(II)
and Related Complexes
On the Orbital Nature of the Luminescent Excited State of Orthometal
ated Transition Metal Complexes
VIII
(v. Balzani, M. Maestri, A. Meiandri, D. Sandrini, L. Chassot,
C. Cornioley-Deuschel, P. Jolliet, U. Maeder, A. von Zelewsky) .•..• 71
Correlations Between Optical and Electrochemical Properties of Ru(II)
Polypyridine Complexes: Influence of the Ligand Structure
(F. Barigelletti, A. Juris, V. Balzani, P. Belser, A. von Zelewsky) 79
Towards a Dynamic Model for the Ru(hpy) 32+ System
(M.A. Collins, E. Krausz) ..........•..•..•.•.•..............••.•.. 85
Broad-Band Emission and Zero-Phonon Lines of Single-Crystal
[Ru(bpy)3] (PF6)2 - A Comparison
(E. Gallhuber, G. Hensler, H. Yersin) .........•.•.•........•••.... 93
Magnetic-Field Effects and Highly Resolved Vibronic Structure of
t~~(~~~~ll~+E.
Gallhuber, G. Hensler) .....•.............•....•..• 101
Highly Resolved Optical Spectra of [os(bpY)312+ Doped into
[Ru (bpy) 31 X2
(G. Hensler, E. Gallhuber, H. Yersin) 107
Excited State Behaviors of Ruthenium(II) Complexes as Studied by Time
Resolved and Temperature and Solvent Dependent Emission Spectra
(S. Tazuke, H.-B. Kim, N. Kitamura) •..........•......•.......•..• 113
The Lowest Excited States of [Ru(2,2'-Bipyrazine) (2,2'-Bipyridine) 2]2+
(H. Kobayashi, Y. Kaizu, K. Shinozaki, H. Matsuzawa) .•..•...•.... 119
Quenching of Excited Ru(bpy) 32+ with Methylviologen at Low Tempera
tures
(Cz. Stradowski, M. Wolszczak) 125
Kinetics of the Chemiluminescent Oxidation of Aqueous Br- by
Ru (bipyr) 33+
.......
(L. El-Sayed, D. Salkin Swaim, W.K. Wilmarth, A.W. Adamson) 129
Synthesis and Photophysical Studies of Ortho-Metalated Pd(II) Com
plexes Including Two Novel Pd(II)!Rh(III) Dimers
(C.A. Craig, F.O. Garces, R.J. Watts) ............•.....•......... 135
Photoproperties of Ortho-Metalated Ir(III) and Rh(III) Complexes
(K.A. King, F. Garces, S. Sprouse, R.J. Watts) •.••..•....•..•.... 1 41
Ground and Excited State Interactions in Multimetal Systems
(J • D. Petersen) ••••••..•.•....••....••.••.....••.......•.•....••. 147
Photophysical and Photochemical Properties of Ruthenium (II) Mixed
Ligand Complexes: Precursors to Homonuclear and Heteronuclear Multi
metal Complexes Containing Ruthenium (II) , Platinum(II), Rhenium (I)
and Rhodium (III)
(D.P. Rillema, H.B. Ross) 151
Ground- and Excited-State Acid-Base Equilibria of (2,2'-Bipyridine)
Tetracyanoruthenate(II)
(M.T. Indelli, C.A. Bignozzi, A. Marconi, F. Scandola) .......••.• 159
Topic 4: Photoredox Processes
Kinetics and Mechanism of Photochemical Formation of a Pyrazine
Bridged Fe(II) Protoporphyrin IX Polymeric Compound
(C. Bartocci, A. Maldotti, R. Amadelli, V. Carassiti) 167
IX
Charge-Transfer States and Two-Photon Photochemistry of Cu(NN)2+
Systems
(R.M. Berger, A.K. Ichinaga, D.R. McMillin) •••.•••••••.•••.••••••• 171
Photoinduced Multielectron Redox Reactions in the [ptct6J2-jAlcohol
System: Visible Light Reduction of Platinum Centers
(A.B. Bocarsly, R.E. Cameron, M. Zhou) .••••••••.•••••••.••••••••. 177
Dynamic and Static Outer-Sphere and Inner-Sphere Quenching Processes
(L. Checchi, C. Chiorboli, M.A. Rampi Scandola, F. Scandola) ••••• 181
Photochemistry and Spectroscopy of Ion Pair Charge Transfer Compounds
(H. Hennig, D. Rehorek, R. Billing) ••••.••••••••••.••••••••.••••• 185
Backward Electron Transfer within Geminate Radical Pair Formed in the
Electron Transfer Quenching
(T. Ohno, A. Yoshimura) •••••••••••••••••••••••••••••••••••••••••• 189
Photochemistry of Copper Complexes and its Catalytic Aspects
(J. Sykora) ••••••••••••••••••••••••..••.•••...••••.•••••••••.•••• 193
Intramolecular Excited State Electron Transfer from Naphthalene to
Cobalt (III) ~
(A.H. Osman, A. Vogler) 197
Photochemistry of Coordination Compounds of Main Group Metals.
Reductive Elimination of Thallium(III) Complexes ~
(A. Paukner, H. Kunkely, A. Vogler) ••••••••.•.•••••••••••.••••••• 205
Topic 5: Organometallic Photochemistry
Photophysics and Photochemistry of Tungsten Carbyne Complexes
(A.B. Bocarsly, R.E. Cameron, A. Mayr, G.A. McDermott) ••••••••••• 213
The Photoisomerization and Photosubstitution Reactions of the Ruthe
nium Cluster HRu3(CO)1o(~-COCH3)
(A.E. Friedman, P.C. Ford) ••••••••••••.•••.•••••••••••••••••••••• 217
Multiple Emission from (~5-C5H5)Re(CO)2L (L = a Substituted Pyridine)
Complexes in Room-Temperature Solution
(M.M. Glezen, A.J. Lees) ••••••.••••••••••••••••••••••••.••••••••• 221
Photochemically Induced C-C-Bond Formation in the Coordination Sphere
of Transition Metals
(C.G. Kreiter, K. Lehr) 225
Triplet Quenching by Metal Carbonyls
(M. Kucharska-Zon, A.J. Poe) ••••••••••••••••••••••••••••••••••••• 231
Photoexcitation of W(CO)6 Solutions Containing ~-Diimine Ligands.
Kinetics and Mechanism of Chelation for a Series of Photoproduced
W(CO)5(~-Diimine) Intermediates
(A.J. Lees, M.J. Schadt, L. Chan) 235
Kinetics and Mechanism of C-H Activation Follo*w ing Photoexcitation
of (T)5_C5H5) Ir(CO) 2 in Hydrocarbon Solutions
(D.E. Marx, A.J. Lees) ••••••••.•.•••••••••••••••••••••••••••••.•• 239
Identification of H2-, D2-' N2-Bonded Intermediates in the Cr(CO)6
Photocatalyzed Hydrogenation Reactions
(A. Oskam, R.R. Andrea, D.J. Stufkens, M.A. Vuurman) ••••••••••••• 243
x
Spectroscopy and Photochemistry of Ni(CO)2(~-Diimine) Complexes
(P.C. Servaas, D.J. Stufkens, A. Oskarn) .••.............••.•..•... 247
Fe(CO)3(R-DAB), a Complex with Two Close-Lying Reactive Excited
States
(D.J. Stufkens, H.K. van Dijk, A. Oskarn) 253
The Photocatalytic Metathesis Reaction of Olefins
(T. Szymanska-Buzar, J.J. Zi6):kowski) .•.•...........•.......••••. 259
Photochemical Generation of Nineteen-Electron Organometallic Complexes
and Their Use as Reducing Agents in Micellar Systems
(D.R. Tyler, V. MacKenzie, A.S. Goldman) .......•..•.••........... 263
Probing Organometallic Photochemical Mechanisms with Quinones:
Photolysis of Mn2(CO)10
(A. Vl~ek, Jr.) •••••••..•.•.••.•...••....•.....•.•..•••..•..••... 267
Laser Flash Photolysis of Phosphine-Substituted Dimanganese Carbonyl
Compounds
(K. Yasufuku, N. Hiraga, K. Ichimura, T. Kobayashi) •.........•.•• 271
Topic 6: Methods, Applications, and Other Aspects
Electron Trapping in Colloidal Ti02 Photocatalysts: 20 ps to 10 ns
Kinetics
(C. Arbour, O.K. Sharma, C.H. Langford) 277
The Radiation Sensitivity of Select Metal Chelate Polymers:
Mechanistic Changes at Higher Energies
(R.D. Archer, C.J. Hardiman, A.Y. Lee) 285
Temperature Dependent Emission of Copper Porphyrins in Liquid Solution
(M. Asano, O. Ohno, Y. Kaizu, H. Kobayashi) . • . . • • • . . • . . • . . . • . . • .. 291
Pressure Effects on Nonradiative Deactivation from Metal Complex
Excited States in Solution
(P.C. Ford, J. DiBenedetto) 295
Heterogeneous Photocatalysis by Metal Sulfide Semiconductors
(H. Kisch, W. Hetterich, G. Twardzik) •.••...••...•.•..•..•...•..• 301
*
Inorganic Photoinitiators for Photolithographic Applications
(C. Kutal, C.G. Willson) •.•..•.••.....•..........••..........•... 307
Photochemical Behaviour of Luminescent Dyes in Sol-Gel and Boric
Acid Glasses
(R. Reisfeld, M. Eyal, R. Gvishi, C.K. J¢rgensen) 313
Industrial Applications of Organometallic Photochemistry
(A. Roloff, K. Meier, M. Riediker) •••..••...•..•...•...•.••.....• 317
Synthesis and Characterization of a ~-oxo-diruthenium Complex as a
Precursor to an Efficient Water Oxidation Catalyst
(F.P. Rotzinger, S. Munavalli, P. Comte, J.K. Hurst, M. Gratzel) 323
The Application of Diffuse Reflectance Laser Flash Photolysis to
Metal Phthalocyanines in an Opaque Environment
(F. Wilkinson, C.J. Willsher) ..•.•.....•.••......•.....•••.•..•.. 327
Quenching of Singlet Oxygen by Cobalt Complexes
(T. Vid6czy, S. Nemeth) •..•...••..••••.•••.....•.•...•....•.••... 331
XI
Recent Advances in Inorganic and Organometallic Photolithograph~
(R.E. Wright) ••••••••••••••••••••••••••••••••••••••••••••••••••••• 335
Author Index ••••••••••••••••••••••••••••••••••••••••.•••••••••••• 339
*Contributions marked with an asterix (*) are dedicated to
Prof. A.W. Adamson by his former graduate students and post doctoral
associates.
TOPIC 1
Metal-Centered Excited States
