Manganese(iii) Complexes
3757 3768
10 mm  30 mm platinum grid (400 mesh per cm2) was used as working
electrode. The counter and reference electrodes were as described in the
Electrochemistry section above.
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Solvent-saturated argon was bubbled into the samples for 20 min and they
were then transferred with the argon current to the argon-flushed cell. The
spectra were recorded on
(Hewlett Packard 8435).
a UV/Vis diode array spectrophotometer
EPR spectroscopy: EPR measurements were performed on a Bruker E500
X-band spectrometer equipped with a dual-mode cavity and an Oxford
Instruments ESR900 flow cryostat. Complexes 1a and 2a were dissolved to
1mm in dry acetonitrile and frozen in liquid nitrogen before measurements.
Spectrometer settings were modulation frequency 100 kHz, modulation
amplitude 10 G; all spectra were taken at 4 K. See the figure legends for
further details.
Flash photolysis: Flash photolysis measurements with optical transient
absorption detection were performed with a laser flash photolysis set-up
consisting of a Nd:YAG laser/OPO combination (Quantel) and a flash
photolysis spectrometer (Applied Photophysics). The samples were excited
at 460 nm with an energy of 30 mJ per 5 ns pulse. MnIIIL (0.1 1mm) was
disolved in acetonitrile (Merck, spectroscopy grade) containing Ru(b-
py)3(PF6)2 (ꢀ40mm, Abs460 0.6) and methylviologen hexafluorophos-
phate (20mm) or p-benzoquinone (10mm, Fluka, ꢁ99.5%). The bimolec-
ular rate constant of the reaction of MnIII
L
with [Ru(bpy)3]3 was
determined from a pseudo first-order plot of the recovery rate for
[Ru(bpy)3]2 observed at 450 nm with methylviologen as quencher. To
avoid the intense and broad absorption of the reduced methylviologen,
transient spectra were recorded with p-benzoquinone as acceptor. Oxygen
was removed by bubbling with solvent-saturated nitrogen.
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Acknowledgements
We thank Professor S. Styring, Lund, and Professor J. J. Girerd, Orsay, for
stimulating discussions. Financial support from the following agencies is
gratefully acknowledged: Knut and Alice Wallenberg Foundation, the
Swedish National Energy Administration, the Delegation for Energy
Supply in South Sweden (DESS), the Swedish Natural Science Research
Council (NFR), the Swedish Research Council for Engineering Sciences
(TFR) and the European TMR Program (TMR network CT96 0031).
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