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ChemComm
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COMMUNICATION
Journal Name
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Intercluster Interactions in Transition Metal Cluster
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DOI: 10.1039/C7CC00516D
21 For the electrochemically generated 22+ (in CH2Cl2 + 0.1 M
TBAP) a new broad feature is observed at g ~ 2, associated to
a shoulder at g ~ 4 (150 mT) in the temperature range 6-20
K. These features are indicative of a high spin state. This
signal is not detected when a chemically generated sample is
dissolved in neat CH2Cl2, while it is barely visible for
microwave powers larger than 20 mW and 6 K when a
chemically generated sample of 22+ 2 SbF6- is dissolved in
CH2Cl2 + 0.1 M TBAP (see ESI). Hence, the interactions
between the counter-ions and the complex (presumably
through the NH groups) likely alter the quartet-doublet
Gellon, C. Philouze, F. Thomas, Chem. Commun., 2014, 50
1918.
,
energy gap and/or the electronic structure of 22+
.
3
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The large Ep measured for the first oxidation wave is
indicative of a proton-coupled to electron transfer.
two low energy electronic
2, 166. (c) R. F. Munha, R. A.
9
10 TD-DFT calculations predict for
2
excitations at 1739.83 nm (fosc = 0.0243) and 1084.53 (fosc
0.0481). For 22+ an electronic excitation is predicted at
1142.31 nm (fosc = 0.0672), which accounts for the NIR tail
=
experimentally observed. The associated Natural Transition
Orbitals (NTOs) are shown in Tables S1 and S2.
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18 The use of a Mn(IV) state as an initial guess converges to the
Mn(V)-radical 4[2]2+ solution.
19 K. Kambe J. Phys. Soc. Jpn 1950, 5, 48.
20 A. P. Ginsberg, M. E. Lines in "Magnetic Exchange in
Transition Metal Complexes. VIII. Molecular Field Theory of
4 | J. Name., 2012, 00, 1-3
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