Dalton Transactions
Paper
Electrochemical measurements
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Cyclic voltammetry (CV) and square wave voltammetry (SWV)
measurements were carried out in CH3CN containing 0.1 M
TBAPF6 as an electrolyte at 298 K under Ar using a BAS
ALS-710D electrochemical analyser with a platinum working
electrode, a platinum wire as a counter electrode, and Ag/
AgNO3 as a reference electrode. The potentials measured were
calibrated to be those relative to SCE by adding 0.29 V.29
ESR measurements
ESR spectra were recorded on a Bruker BioSpin X-band
spectrometer (EMXPlus9.5/2.7) with an ESR900 helium-flow
cryostat (Oxford Instruments) in a quartz tube (o.d. = 4 mm).
The magnitude of the modulation was chosen to optimise the
resolution and the signal to noise (S/N) ratio of the observed
spectrum under non-saturating microwave power conditions
(microwave power, 5.0 mW; modulation amplitude, 15.0 G;
modulation frequency, 100 kHz). An ESR sample of RuIII
species was prepared by mixing 1 (1.0 mM) and 1.0 eq. of
Me8Fc as a reductant in CH3CN at room temperature. After
bubbling He into the prepared solution, the sample solution
was transferred in quartz tubes under He atmosphere.
Computational methods
All calculations were performed by the Gaussian 16 program
package.30 We optimised local minima on the potential energy
using the B3LYP method.31 For the Ru atom, we used the SDD
basis sets,32 and for the H, C, N, O, and F atoms, we used the
D95** basis set.33 Vibration frequencies were systematically com-
puted in order to ensure that on a potential energy surface each
optimised geometry corresponds to a local minimum that has no
imaginary frequency. Solvent effect of acetonitrile was included
using the corresponding polarizable continuum model (PCM).34
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Conflicts of interest
There are no conflicts to declare.
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Acknowledgements
This work was supported by Grants-in-Aid (No. 17H03027 and
17K14456) from the Japan Society of Promotion of Science
(JSPS, MEXT) of Japan and the Cooperative Research Program
of “Network Joint Research Center for Materials and Devices”.
Financial supports through CREST (JST) are also appreciated
(JPMJCR16P1 for T.K. and JPMJCR15P5 for K.Y.). We also
appreciate Dr Takashi Kikuchi (Rigaku Corporation) for
cooperation in X-ray crystallographic analysis on 2.
Notes and references
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J. M. Bollinger, Acc. Chem. Res., 2007, 40, 484–492.
T. Parella and H. Stoeckli-Evans, Inorg. Chem., 2001, 40,
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