Influence of proline in the stabilization of radical cations –
Supporting Information
Nicolas P.-A. Monney, Thomas Bally and Bernd Giese * .
University of Fribourg, Chemin du Musée 9, CH-1700 Fribourg, Switzerland
* Correspondence: Prof. Dr. B. Giese, e-mail: bernd.giese@unifr.ch
Reference
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Table S1: Different vertical ionization energies calculated with M06-2X/6-31G*.
Species Vertical
IE (eV)
Difference
(eV)
Difference
(kcal/mol)
2,4-dimethoxytoluene
1A
1C
2,4,6-trimethoxytoluene
1B toluene neutral neutral
4A
4B
7.73
7.27
7.36
7.48
7.34
8.84
1)
8.34
8.34 neutral 4C
N,N-dimethylacetamide
8.40
8.99
2)
5 8.46
1) 8.83 eV on NIST Webbook of chemistry
2) 9.11 eV from Fig. 7
-0.46
-0.37
-0.14
-0.50
-0.50
-0.45
-0.54
-10.5
-8.5
-3.3
-11.6
-11.6
-10.3
-12.3
Figure S1: Distances between the trimethoxybenzyl ring and both the interacting p-lone pair and the dimethoxybenzyl ring in conformer 3B .

Figure S2: Geometry changes of the interacting groups on one electron oxidation of the conformers A , B and C .
The green structures are those of the neutral conformers.
Figure S3: SOMO of three conformers of PheProPhe 4 .

Figure S4: Superimposition of the two conformers of 5 that participate in the PE spectrum shown in Fig. 7.
Table S2: Lowest Ionization Energies (in eV) of N,N-Dimethylacetamide (DMA) and 5 as shown in Fig. 7.
Compound
DMA
5 experimental
9.1, 9.5
8.5, 8.7, 9.3, 9.4, 11.5 calculated
9.0, 9.2,
8.5, 8.6, 9.2, 9.3, 11.4, 11.7