nitroxides_SI.tex

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\usepackage{siunitx}
\usepackage[version=4]{mhchem}
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\usepackage[square,sort,comma,numbers]{natbib}

\title{Solvent effects on the prediction of redox potentials: application to nitroxides\\ Supporting information}
\author{Pierre Beaujean}
\begin{document}
\maketitle


\renewcommand{\thetable}{S\arabic{table}}
\renewcommand{\thefigure}{S\arabic{figure}}

\begin{figure}[!h]
	\centering
	\includegraphics [width=\linewidth]{FigureS1}
	\caption{Evolution of (left) the Born solvation energy, $\Delta G^\star_{Born}$ [computed with Eq.~(7)] as a function of the dielectric constant of the solvent for different radii of  the spherical cavities ($a$) and of (right) the Debye-Hückel correction, $\Delta G^\star_{DH}$  [computed with Eq.~(5)] as a function of the concentration in electrolyte, $[X]$, in water and acetonitrile.}
\end{figure}

\begin{figure}[!h]
\centering
\includegraphics [width=.5\linewidth]{FigureS2}
\caption{Impact of the concentration of electrolyte on the formal oxidation potential [computed with Eq.~(10)] , $E^f_{abs}(\ce{N+}|\ce{N^.})$, considering a fictitious case where $E^0_{abs} = \SI{0}{\volt}$.}
\end{figure}

\begin{figure}[!h]
\centering
\includegraphics [width=.7\linewidth]{FigureS3}
\caption{Evolution of the cologarithm of the equilibrium constant, $pK_{pair}$ [computed from Eq.~(12)] between two ions as a function of $\chi$, the ratio between the radii of the two ions and for 3 values of dipole cavity shape factor ($s_2$). The ion charges are set to $\pm 1$, and two possible scaling factors for  the close contact distance are used ($s_1$, left and right). }
\end{figure}


\begin{figure}[!h]
	\centering
	\includegraphics [width=.7\linewidth]{FigureS4}
	\caption{Comparison between the absolute oxidation (top) and reduction (bottom) potentials obtained by Hodgson \emph{et al.} (at the G3(MP2)-RAD:MP2/6-311+G(3df,2p) level, using solvation energy computed at the B3LYP/6-31G(d) level in water [CPCM]) \cite{hodgsonOneElectronOxidationReduction2007}, and in this work (at the $\omega$B97X-D/6-311+G(d) level in water [SMD]). The DH correction has \textbf{not} been applied. The large differences (e.g., for the oxidation of APOs) are due to change in geometries after re-optimization at the DFT level. The dashed line is a linear regression, from which points marked with triangle ($\blacktriangle$) have been excluded.}
\end{figure}

\clearpage
\begin{longtblr}[caption={Radii ($a$, in \si{\angstrom}) for all oxidized states of compounds \textbf{1}-\textbf{61} and corresponding absolute redox potentials ($E^0_{abs}$, in \si{\volt}), as computed at the $\omega$B97X-D/6-311+G(d) level in water (SMD), in the limit of  $[\ce{X}]=\SI{0}{\mole\per\liter}$.}]{colspec={>{\bfseries}lX[c]X[c]X[c]X[c]X[c]},width = 0.85\linewidth, rowhead=1}
	\hline
	& $a_{\ce{N+}}$ & $a_{\ce{N^.}}$ & $a_{\ce{N-}}$ & $E^0_{abs}(\ce{N+}|\ce{N^.})$ & $E^0_{abs}(\ce{N^.}|\ce{N-})$\\
	\hline
	1 & 3.40 & 3.38 & 3.39 & 5.00 & 2.88\\
	2 & 3.33 & 3.30 & 3.34 & 5.09 & 2.97\\
	3 & 3.92 & 3.91 & 3.90 & 5.17 & 3.03\\
	4 & 3.36 & 3.35 & 3.35 & 5.13 & 3.00\\
	5 & 3.91 & 3.91 & 3.91 & 5.18 & 3.00\\
	6 & 3.31 & 3.30 & 3.34 & 5.18 & 3.02\\
	7 & 4.27 & 4.47 & 4.46 & 5.09 & 2.77\\
	8 & 4.06 & 4.05 & 4.06 & 5.19 & 3.04\\
	9 & 4.05 & 4.04 & 4.05 & 5.29 & 3.13\\
	10 & 4.16 & 4.16 & 4.16 & 5.32 & 3.14\\
	11 & 3.37 & 3.36 & 3.36 & 5.29 & 3.10\\
	12 & 3.33 & 3.31 & 3.34 & 5.30 & 3.14\\
	13 & 3.28 & 3.30 & 3.34 & 5.14 & 2.99\\
	14 & 3.27 & 3.27 & 3.24 & 5.08 & 2.84\\
	15 & 3.57 & 3.82 & 3.74 & 5.26 & 2.95\\
	16 & 3.27 & 3.26 & 3.24 & 5.15 & 2.89\\
	17 & 3.47 & 3.48 & 3.85 & 5.13 & 2.91\\
	18 & 3.25 & 3.25 & 3.24 & 5.15 & 2.95\\
	19 & 4.20 & 4.19 & 4.33 & 5.11 & 2.76\\
	20 & 3.81 & 3.81 & 3.81 & 5.33 & 3.03\\
	21 & 3.27 & 3.24 & 3.23 & 5.28 & 3.17\\
	22 & 3.24 & 3.23 & 3.18 & 5.35 & 3.10\\
	23 & 3.60 & 3.60 & 3.62 & 5.27 & 2.96\\
	24 & 4.58 & 4.58 & 4.62 & 5.29 & 3.07\\
	25 & 4.05 & 4.02 & 4.01 & 5.23 & 2.96\\
	26 & 4.65 & 4.66 & 4.69 & 5.23 & 2.98\\
	27 & 3.94 & 3.94 & 3.98 & 5.24 & 2.99\\
	28 & 5.01 & 5.00 & 5.07 & 5.24 & 2.79\\
	29 & 4.30 & 4.29 & 4.24 & 5.28 & 3.08\\
	30 & 4.32 & 4.32 & 4.35 & 5.36 & 3.12\\
	31 & 4.61 & 4.60 & 4.62 & 5.32 & 3.12\\
	32 & 4.57 & 4.57 & 4.58 & 5.34 & 3.11\\
	33 & 4.63 & 4.64 & 4.65 & 5.34 & 3.04\\
	34 & 4.69 & 4.71 & 4.24 & 5.27 & 3.01\\
	35 & 4.05 & 4.04 & 4.07 & 5.34 & 3.06\\
	36 & 4.13 & 4.14 & 4.13 & 5.24 & 3.10\\
	37 & 4.58 & 4.62 & 4.61 & 5.26 & 3.15\\
	38 & 5.21 & 5.18 & 5.00 & 5.30 & 3.08\\
	39 & 5.10 & 5.09 & 5.11 & 5.30 & 3.15\\
	40 & 5.19 & 5.10 & 5.17 & 5.31 & 3.19\\
	41 & 5.09 & 5.05 & 5.06 & 5.29 & 3.21\\
	42 & 5.08 & 5.12 & 5.00 & 5.33 & 3.08\\
	43 & 5.47 & 5.49 & 5.68 & 5.31 & 3.15\\
	44 & 5.32 & 5.41 & 5.46 & 5.29 & 3.22\\
	45 & 5.21 & 4.90 & 4.98 & 5.31 & 3.19\\
	46 & 5.14 & 5.17 & 5.15 & 5.32 & 3.16\\
	47 & 5.22 & 5.22 & 5.55 & 5.29 & 3.13\\
	48 & 5.12 & 5.13 & 4.79 & 5.31 & 3.16\\
	49 & 4.13 & 4.14 & 4.14 & 5.14 & 3.07\\
	50 & 4.56 & 4.52 & 4.57 & 5.24 & 3.08\\
	51 & 4.52 & 4.50 & 4.49 & 5.19 & 3.06\\
	52 & 4.11 & 4.12 & 4.12 & 5.35 & 3.19\\
	53 & 4.74 & 4.71 & 4.68 & 5.36 & 3.13\\
	54 & 4.63 & 4.64 & 4.65 & 5.33 & 3.17\\
	55 & 4.67 & 4.68 & 4.67 & 5.41 & 3.23\\
	56 & 3.80 & 3.85 & 3.88 & 5.18 & 2.76\\
	57 & 3.57 & 3.54 & 3.60 & 5.07 & 2.89\\
	58 & 3.67 & 3.65 & 3.64 & 5.31 & 2.78\\
	59 & 3.63 & 3.62 & 3.65 & 5.20 & 2.91\\
	60 & 4.01 & 4.00 & 4.01 & 5.31 & 3.04\\
	61 & 3.31 & 3.30 & 3.34 & 5.20 & 3.06\\
	\hline
\end{longtblr}

\clearpage
\begin{longtblr}[caption={Absolute redox potentials ($E^0_{abs}$, in \si{\volt}) computed at the $\omega$B97X-D/6-311+G(d) level in gas phase.}]{colspec={>{\bfseries}lX[c]X[c]c>{\bfseries}lX[c]X[c]},width = 0.85\linewidth, rowhead=1}
\hline
& $E^0_{abs}(\ce{N+}|\ce{N^.})$ & $E^0_{abs}(\ce{N^.}|\ce{N-})$ &&& $E^0_{abs}(\ce{N+}|\ce{N^.})$ & $E^0_{abs}(\ce{N^.}|\ce{N-})$\\
\hline
1  & 6.69 & 0.18 &  & 32 & 7.22 & 0.57 \\ 
2 & 7.01 & 0.23 &  & 33 & 7.33 & 0.60 \\ 
3 & 7.16 & 0.41 &  & 34 & 6.98 & 0.32 \\ 
4 & 7.06 & 0.31 &  & 35 & 9.93 & 3.04 \\ 
5 & 7.09 & 0.33 &  & 36 & 7.04 & 0.52 \\ 
6 & 7.12 & 0.40 &  & 37 & 6.97 & 0.65 \\ 
7 & 6.89 & 0.41 &  & 38 & 7.12 & 0.67 \\ 
8 & 7.15 & 0.46 &  & 39 & 7.11 & 0.73 \\ 
9 & 7.28 & 0.64 &  & 40 & 6.99 & 0.75 \\ 
10 & 7.27 & 0.69 &  & 41 & 7.06 & 0.82 \\ 
11 & 10.41 & 3.54 &  & 42 & 7.07 & 0.74 \\ 
12 & 7.40 & 0.63 &  & 43 & 7.07 & 0.78 \\ 
13 & 7.08 & 0.23 &  & 44 & 7.00 & 0.75 \\ 
14 & 7.04 & 0.03 &  & 45 & 7.17 & 0.78 \\ 
15 & 7.20 & 0.29 &  & 46 & 7.17 & 0.85 \\ 
16 & 7.01 & 0.14 &  & 47 & 7.19 & 0.81 \\ 
17 & 6.95 & 0.13 &  & 48 & 7.20 & 0.88 \\ 
18 & 7.01 & 0.33 &  & 49 & 6.80 & 0.51 \\ 
19 & 6.93 & 0.36 &  & 50 & 6.91 & 0.49 \\ 
20 & 7.30 & 0.50 &  & 51 & 6.76 & 0.46 \\ 
21 & 10.82 & 6.26 &  & 52 & 7.20 & 0.82 \\ 
22 & 7.37 & 0.31 &  & 53 & 7.34 & 0.87 \\ 
23 & 7.12 & 0.28 &  & 54 & 7.32 & 0.92 \\ 
24 & 7.25 & 0.47 &  & 55 & 7.62 & 1.26 \\ 
25 & 6.93 & 0.19 &  & 56 & 6.91 & 0.22 \\ 
26 & 7.02 & 0.24 &  & 57 & 6.88 & 0.15 \\ 
27 & 7.08 & 0.29 &  & 58 & 7.22 & 0.24 \\ 
28 & 7.00 & 0.44 &  & 59 & 7.03 & 0.06 \\ 
29 & 7.06 & 0.35 &  & 60 & 7.26 & 0.45 \\ 
30 & 6.98 & 0.51 &  & 61 & 7.28 & 0.57 \\ 
31 & 7.17 & 0.55 &  &  &  &  \\ 
\hline
\end{longtblr}

\clearpage
\begin{longtblr}[caption={Radii ($a$, in \si{\angstrom}) for all oxidized states of the compounds and corresponding absolute redox potentials ($E^0_{abs}$, in \si{\volt}), as computed at the $\omega$B97X-D/6-311+G(d) level in acetontrile (SMD), with $[\ce{X}]=\SI{0}{\mole\per\liter}$.}]{colspec={>{\bfseries}lX[c]X[c]X[c]X[c]X[c]},width = 0.85\linewidth, rowhead=1}
	\hline
	& $a_{\ce{N+}}$ & $a_{\ce{N^.}}$ & $a_{\ce{N-}}$ & $E^0_{abs}(\ce{N+}|\ce{N^.})$ & $E^0_{abs}(\ce{N^.}|\ce{N-})$\\
	\hline
2 & 3.33 & 3.30 & 3.35 & 4.99 & 2.32\\
3 & 3.92 & 3.91 & 3.90 & 5.15 & 2.37\\
4 & 3.36 & 3.36 & 3.35 & 5.06 & 2.34\\
6 & 3.31 & 3.30 & 3.35 & 5.11 & 2.37\\
12 & 3.33 & 3.31 & 3.34 & 5.27 & 2.46\\
15 & 3.58 & 3.81 & 3.74 & 5.20 & 2.30\\
23 & 3.61 & 3.60 & 3.62 & 5.24 & 2.33\\
24 & 4.59 & 4.57 & 4.62 & 5.27 & 2.37\\
25 & 4.05 & 4.03 & 4.02 & 5.19 & 2.30\\
26 & 4.65 & 4.65 & 4.68 & 5.22 & 2.31\\
27 & 3.95 & 3.94 & 3.98 & 5.23 & 2.32\\
33 & 4.63 & 4.64 & 4.65 & 5.28 & 2.42\\
36 & 4.13 & 4.12 & 4.08 & 5.19 & 2.51\\
51 & 4.53 & 4.50 & 4.47 & 5.12 & 2.47\\
54 & 4.61 & 4.62 & 4.63 & 5.33 & 2.58\\
55 & 4.68 & 4.68 & 4.62 & 5.40 & 2.68\\
58 & 3.66 & 3.65 & 3.64 & 5.24 & 2.12\\
59 & 3.62 & 3.61 & 3.65 & 5.14 & 2.27\\
60 & 4.01 & 3.99 & 4.02 & 5.28 & 2.36\\
61 & 3.31 & 3.30 & 3.34 & 5.15 & 2.42\\
	\hline
\end{longtblr}

\clearpage

\begin{figure}[!h]
	\centering
	\begin{tblr}{lccc}
		\hline
		& $\sigma_p$ & $\sigma_m$ & $\sigma_I$ \\
		\hline
		\ce{COOH} & 0.45 &0.37 &--- \\
		\ce{NH2} & -0.66 & -0.16 & 0.10\\
		\ce{OMe} & -0.27 & 0.12 & 0.23\\
		\ce{OH} & -0.37 & 0.12 &0.27\\
		\ce{NH3+} & 0.60 & 0.86 &---\\
		\ce{Br} & 0.23 & 0.39 & 0.45\\
		$>$\ce{C=O} & 0.50 & --- & --- \\
		\ce{C=C-CONH2} & 0.36 & 0.28 & --- \\
		\ce{NO2} & 0.78 & 0.71 & 0.63 \\
		\hline
	\end{tblr}
	\includegraphics [width=\linewidth]{FigureS5}
	\caption{Correlation between absolute oxidation (left) and reduction (right) as computed at the $\omega$B97X-D/6-311+G(d) level in water (SMD) and the Hammet  (top, $\sigma_p$ for P6O and $\sigma_m$ for P5O) or the inductive  (bottom, $\sigma_I$)  constant of their substituent for compounds of the P5O (black markers, correlated with $\sigma_m$) and P6O (blue markers, correlated with $\sigma_p$) families. All constants are obtained from Ref.~\cite{hanschSurveyHammettSubstituent1991}.}
\end{figure}

\clearpage

\begin{longtblr}[caption={Distance ($r$, in \si{\angstrom}), $x$-component of the dipole moment  ($\mu_x$, in \si{\elementarycharge\bohr}) and $xx$ component of the traceless quadrupole moment  ($Q_{xx}$, in \si{\elementarycharge\bohr\squared}) for all compounds, as computed at the $\omega$B97X-D/6-311+G(d) level in gas phase for model geometries ($>$\ce{N-O^.} replaced by \ce{CH2}, see main text) }]{colspec={>{\bfseries}lX[c]X[c]X[c]}, width = 0.85\linewidth, rowhead=1}
	\hline
	& $r$ & $\mu_x$ & $Q_{xx}$\\
	\hline
	2 & 2.87 & -0.05 & -0.06\\
	3 & 2.87 & 0.29 & 3.36\\
	4 & 2.89 & 0.33 & -1.26\\
	5 & 2.87 & 0.19 & 0.99\\
	6 & 2.87 & 0.73 & -2.41\\
	7 & 2.86 & 0.35 & 3.14\\
	8 & 2.86 & 0.29 & 1.94\\
	9 & 2.86 & 0.63 & 3.10\\
	10 & 2.85 & 0.80 & -0.49\\
	12 & 2.83 & 1.28 & -1.44\\
	13 & 2.80 & 0.06 & 0.64\\
	14 & 2.20 & -0.02 & -0.03\\
	15 & 2.20 & 0.29 & 2.22\\
	16 & 2.20 & 0.42 & -2.33\\
	17 & 2.21 & -0.33 & 1.09\\
	18 & 2.21 & -0.03 & 0.10\\
	19 & 2.20 & 0.34 & 1.26\\
	20 & 2.19 & 0.77 & 0.35\\
	22 & 2.15 & 0.62 & -0.24\\
	23 & 2.19 & 0.17 & 2.74\\
	24 & 2.19 & 0.61 & 7.84\\
	25 & 2.19 & -0.27 & 2.42\\
	26 & 2.19 & 0.18 & 1.13\\
	27 & 2.19 & 0.03 & 3.80\\
	28 & 2.18 & 0.60 & 7.36\\
	29 & 2.19 & -0.01 & 4.95\\
	30 & 2.18 & -0.36 & 3.30\\
	31 & 2.18 & -0.11 & 11.49\\
	32 & 2.19 & 0.70 & 5.41\\
	33 & 2.18 & 1.14 & 6.51\\
	34 & 2.19 & -0.22 & 5.34\\
	36 & 2.81 & 0.26 & 4.61\\
	37 & 2.81 & 0.31 & 5.55\\
	38 & 2.82 & 0.50 & 9.83\\
	39 & 2.83 & 0.77 & 8.60\\
	40 & 2.81 & 0.68 & 7.29\\
	41 & 2.81 & 0.45 & 12.13\\
	42 & 2.82 & 0.96 & 5.67\\
	43 & 2.81 & -0.43 & 1.02\\
	44 & 2.81 & -0.07 & 5.29\\
	45 & 2.82 & 1.42 & 4.35\\
	46 & 2.83 & 0.25 & 10.50\\
	47 & 2.81 & -0.17 & 7.36\\
	48 & 2.82 & 1.19 & 10.49\\
	49 & 2.79 & -0.21 & 4.30\\
	50 & 2.82 & -0.15 & 4.82\\
	51 & 2.82 & -0.16 & 4.23\\
	52 & 2.81 & 1.01 & 7.74\\
	53 & 2.82 & 2.18 & 3.27\\
	54 & 2.83 & 2.37 & 2.41\\
	55 & 2.83 & 3.96 & 6.84\\
	56 & 2.22 & -0.19 & 2.94\\
	57 & 2.21 & 0.36 & -3.39\\
	58 & 2.19 & 0.28 & 2.91\\
	59 & 2.19 & -0.15 & 2.12\\
	60 & 2.19 & 0.98 & 2.98\\
	61 & 2.85 & 1.01 & -0.94\\
	\hline
\end{longtblr}


\clearpage
\begin{longtblr}[caption={Distances ($d$, in \si{\angstrom}) between $>$\ce{N+=O} and \ce{A-} (left, measured as the distance between the nitrogen and the boron of \ce{A-}) and between \ce{N-O-} and \ce{C+} (right, measured as the distance between the oxygen and the nitrogen of \ce{C+}) together with their corresponding Gibbs free energy of complexation ($\Delta G^\star_{cplx}$, in \si{\kilo\joule\per\mole}) in two different cases: in front of the methyls ($f$, near the redox center) and behind the methyls ($b$, near the substituent), as computed at the $\omega$B97X-D/6-311+G(d) level in water (SMD), with $[\ce{X}]=\SI{0}{\mole\per\liter}$.}]{colspec={>{\bfseries}lX[c]X[c]X[c]X[c]cX[c]X[c]X[c]X[c]}, width = \linewidth,rowhead=2}
\hline
&  \SetCell[c=4]{c} \ce{N+A-} & & & & &  \SetCell[c=4]{c} \ce{N^-C+} &  & & \\ 
\cline{2-5} \cline{7-10}
& $d_f$ &  $\Delta{G}_{cplx,f}^\star$ &  $d_b$ &  $\Delta{G}_{cplx,b}^\star$ &&  $d_f$ &  $\Delta{G}_{cplx,f}^\star$ & $d_b$ &  $\Delta{G}_{cplx,b}^\star$\\
\hline
2 & 4.041 & 20.8 & 4.127 & 17.6 &  & 4.133 & 39.6 & 4.376 & 38.7 \\
3 & 4.056 & 20.8 & 4.068 & 18.2 &  & 3.832 & 38.8 & 4.064 & 38.5 \\
4 & 4.046 & 18.4 & 4.699 & 14.5 &  & 3.915 & 38.9 & 4.146 & 34.1 \\
5 & 4.059 & 15.0 & 4.056 & 16.5 &  & 3.766 & 37.5 & 4.262 & 29.8 \\
6 & 4.491 & 20.9 & 4.870 & 13.9 &  & 3.913 & 38.6 & 4.159 & 37.1 \\
7 & 4.396 & 20.5 & 4.771 & 18.7 &  & --- & --- & 3.867 & 32.6 \\
8 & 4.000 & 22.0 & 5.749 & 18.6 &  & 4.072 & 47.9 & 4.706 & 41.8 \\
9 & 4.037 & 23.4 & 4.869 & 22.7 &  & 4.330 & 50.8 & 3.737 & 47.8 \\
10 & 4.103 & 25.7 & 5.920 & 17.7 &  & 4.535 & 40.0 & 4.087 & 40.2 \\
11 & --- & --- & 4.865 & 6.7 &  & 3.805 & 36.8 & 4.070 & 32.7 \\
12 & --- & --- & 4.010 & 14.2 &  & 3.830 & 34.4 & 4.433 & 27.6 \\
13 & 3.836 & 21.6 & 5.269 & 20.6 &  & 4.261 & 14.7 & 6.505 & 16.7 \\
14 & 4.250 & 19.0 & 5.401 & 19.4 &  & 4.097 & 17.1 & 7.081 & 17.9 \\
15 & 4.069 & 26.6 & --- & --- &  & 3.894 & 13.8 & 7.129 & 27.5 \\
16 & 4.203 & 24.3 & --- & --- &  & 4.876 & 30.4 & 6.732 & 18.7 \\
17 & 4.064 & 16.9 & 5.672 & 22.7 &  & 4.657 & 18.3 & 7.120 & 8.6 \\
18 & 4.072 & 21.3 & --- & --- &  & 4.865 & 24.8 & 7.515 & 27.4 \\
19 & 4.450 & 35.9 & 5.626 & 35.1 &  & 3.697 & 21.2 & 5.827 & 17.0 \\
20 & 4.182 & 54.5 & --- & --- &  & 3.898 & 25.6 & 6.681 & 22.8 \\
21 & 4.142 & 18.1 & 5.137 & 13.9 &  & 4.120 & 13.9 & --- & --- \\
22 & 4.001 & 20.0 & 5.511 & 20.4 &  & 3.992 & 15.5 & 6.799 & 18.6 \\
23 & 4.207 & 18.7 & 5.009 & 20.5 &  & 4.851 & 17.4 & 6.265 & 8.2 \\
24 & 4.188 & 20.3 & 5.511 & 18.9 &  & 4.201 & 18.2 & 6.616 & 6.5 \\
25 & 4.123 & 19.5 & 5.547 & 19.0 &  & 4.963 & 18.9 & 6.507 & 7.9 \\
26 & 4.115 & 24.9 & 5.574 & 22.7 &  & 4.842 & 19.3 & 6.372 & 8.2 \\
27 & 4.168 & 21.1 & 5.467 & 17.2 &  & 4.793 & 19.0 & 6.314 & 9.6 \\
28 & 4.559 & 15.4 & 5.988 & 15.2 &  & 4.165 & 17.2 & 6.940 & 5.1 \\
29 & 4.257 & 20.5 & 4.770 & 16.8 &  & 3.867 & 20.2 & 6.431 & 9.1 \\
30 & 4.067 & 18.4 & 4.621 & 11.5 &  & 3.871 & 19.1 & 6.405 & 6.3 \\
31 & 4.408 & 20.6 & 4.690 & 18.9 &  & 3.931 & 18.5 & 6.684 & 6.5 \\
32 & 4.030 & 26.8 & 5.098 & 19.7 &  & 3.860 & 20.6 & 6.460 & 4.8 \\
33 & 4.009 & 22.1 & 4.733 & 16.9 &  & --- & --- & 6.164 & 17.2 \\
34 & 4.103 & 17.1 & 5.453 & 16.9 &  & --- & --- & 6.360 & 7.4 \\
35 & 4.113 & 21.0 & 5.817 & 10.4 &  & 4.793 & 24.9 & 6.323 & 10.4 \\
36 & 3.931 & 20.3 & 4.074 & 16.4 &  & 4.547 & 14.2 & 5.653 & 4.7 \\
37 & 4.154 & 19.5 & 4.053 & 17.2 &  & 3.830 & 17.2 & 5.649 & 1.7 \\
38 & 4.297 & 16.6 & 4.036 & 16.0 &  & 3.810 & 13.7 & 6.112 & -2.0 \\
39 & 4.213 & 18.2 & 4.063 & 14.5 &  & 3.823 & 17.5 & --- & --- \\
40 & 4.919 & 15.9 & 5.217 & 12.0 &  & 4.456 & 16.0 & --- & --- \\
41 & 4.086 & 19.7 & 4.051 & 18.4 &  & --- & --- & 6.093 & 3.5 \\
42 & 4.239 & 22.5 & --- & --- &  & 4.273 & 13.9 & 5.308 & -5.5 \\
43 & 4.160 & 18.6 & 4.030 & 16.3 &  & 4.855 & 12.5 & 5.188 & 6.4 \\
44 & 4.237 & 20.9 & 4.103 & 16.2 &  & 4.306 & 19.8 & 6.661 & 6.9 \\
45 & 4.039 & 18.3 & 3.764 & 17.5 &  & 3.773 & 23.4 & 5.456 & 7.0 \\
46 & 4.055 & 20.3 & 5.307 & 14.5 &  & 3.845 & 21.4 & 5.830 & -0.4 \\
47 & 4.265 & 23.4 & 4.047 & 15.0 &  & 4.196 & 15.4 & 5.937 & 4.9 \\
48 & 4.275 & 35.7 & 5.385 & 19.4 &  &  --- &  --- & 6.384 & 15.0 \\
49 & 4.271 & 17.7 & 4.158 & 18.1 &  & 4.798 & 21.4 & 6.293 & -2.4 \\
50 & 4.271 & 18.2 & 4.056 & 17.8 &  & 3.766 & 17.7 & --- & ---  \\
51 & 3.892 & 21.6 & 4.148 & 15.8 &  & 4.781 & 18.2 & 6.006 & 5.2 \\
52 & 3.942 & 19.6 & 3.995 & 11.8 &  & 4.783 & 17.4 & 5.566 & 2.2 \\
53 & 4.252 & 15.7 & 4.088 & 13.7 &  & 3.770 & 19.9 & 5.896 & 7.3 \\
54 & 3.917 & 17.8 & 4.033 & 16.4 &  & 4.794 & 19.2 & 5.822 & -1.1 \\
55 & 4.111 & 17.5 & --- & --- &  & 4.787 & 13.4 & 6.135 & -2.0 \\
56 & 4.070 & 16.2 & --- & --- &  & 4.749 & -14.7 & 5.546 & -8.9 \\
57 & 4.068 & 18.4 & 5.669 & 20.6 &  & 3.895 & 4.2 & 7.126 & 3.6 \\
58 & 4.011 & 21.2 & 4.686 & 17.9 &  & 3.880 & -2.7 & 4.884 & -1.1 \\
59 & 4.051 & 20.4 & 5.054 & 19.2 &  & 3.820 & 16.4 & 4.984 & 16.4 \\
60 & 4.081 & 19.9 & 5.199 & 15.4 &  & 4.580 & 21.1 & 6.352 & 10.0 \\
61 & 3.979 & 24.5 & 4.053 & 20.6 &  & --- & --- & 3.928 & 29.6 \\
\hline
\end{longtblr}

\clearpage
\begin{longtblr}[caption={Distances ($d$, in \si{\angstrom}) between $>$\ce{N+=O} and \ce{A-} (left, measured as the distance between the nitrogen and the boron of \ce{A-}) and between \ce{N-O-} and \ce{C+} (right, measured as the distance between the oxygen and the nitrogen of \ce{C+}) together with their corresponding Gibbs free energy of complexation ($\Delta G^\star_{cplx}$, in \si{\kilo\joule\per\mole}) in two different cases: in front of the methyls ($f$, near the redox center) and behind the methyls ($b$, near the substituent), as computed at the $\omega$B97X-D/6-311+G(d) level in acetonitrile (SMD), with $[\ce{X}]=\SI{0}{\mole\per\liter}$.}]{colspec={>{\bfseries}lX[c]X[c]X[c]X[c]cX[c]X[c]X[c]X[c]}, width = \linewidth,rowhead=2}
\hline
&  \SetCell[c=4]{c} \ce{N+A-} & & & & &  \SetCell[c=4]{c} \ce{N^-C+} &  & & \\ 
\cline{2-5} \cline{7-10}
& $d_f$ &  $\Delta{G}_{cplx,f}^\star$ &  $d_b$ &  $\Delta{G}_{cplx,b}^\star$ &&  $d_f$ &  $\Delta{G}_{cplx,f}^\star$ & $d_b$ &  $\Delta{G}_{cplx,b}^\star$\\
\hline
2 & 3.861 & 20.3 & 4.083 & 16.3 &  & 3.310 & 11.9 & 3.234 & 17.6 \\
3 & 3.870 & 18.9 & 4.078 & 17.7 &  & --- & --- & 3.245 & 11.2 \\
4 & 3.840 & 18.7 & 4.071 & 14.4 &  & 3.313 & 11.6 & 3.260 & 16.8 \\
6 & 3.880 & 17.7 & 4.233 & 14.3 &  & 3.316 & 9.7 & 3.261 & 16.2 \\
12 & --- & --- & 4.011 & 10.7 &  & 3.349 & -2.1 & 3.246 & 3.9 \\
15 & 4.146 & 26.1 & --- & --- &  & 3.358 & -6.8 & 6.286 & 19.4 \\
23 & 4.235 & 20.6 & 5.020 & 20.6 &  & 3.360 & -9.1 & 5.857 & 9.8 \\
24 & 4.093 & 18.7 & 5.566 & 19.8 &  & 3.273 & -0.4 & 6.361 & 10.7 \\
25 & 4.135 & 18.7 & 5.531 & 21.3 &  & 3.263 & 0.4 & 6.493 & 15.1 \\
26 & 4.125 & 21.4 & 5.549 & 21.4 &  & 3.271 & 1.2 & 6.421 & 13.3 \\
27 & 4.211 & 19.8 & 5.375 & 17.8 &  & 3.265 & 0.0 & 6.495 & 12.1 \\
33 & 4.080 & 25.0 & 5.072 & 22.6 &  & 3.278 & -0.1 & 3.321 & 23.2 \\
36 & 4.259 & 19.5 & 4.049 & 16.5 &  & 3.331 & -4.5 & 5.632 & 6.1 \\
51 & 3.942 & 20.8 & 4.128 & 16.7 &  & 3.333 & -5.5 & 5.680 & 0.3 \\
54 & 4.240 & 11.5 & 4.027 & 9.3 &  & 3.337 & -2.2 & 5.624 & 2.6 \\
55 & 4.158 & 14.1 & 4.004 & 13.0 &  & 3.341 & -2.9 & 6.121 & 4.7 \\
58 & 4.187 & 18.8 & 4.885 & 17.0 &  & 3.259 & -21.8 & 4.046 & 13.1 \\
59 & 4.925 & 23.8 & 5.096 & 17.6 &  & 3.361 & -5.2 & --- & --- \\
60 & 4.119 & 19.8 & 5.344 & 20.4 &  & 3.271 & -0.3 & 6.432 & 14.2 \\
61 & --- & --- & 4.055 & 17.0 &  & --- & --- & 3.265 & 12.9 \\
\hline
\end{longtblr}

\clearpage

\begin{longtblr}[caption={Radii ($a$, in \si{\angstrom}) of the ion-pair for the 3 oxidation states of the nitroxides, together with their corresponding Gibbs free energy of complexation ($\Delta G^\star_{cplx}$, in \si{\kilo\joule\per\mole}), as computed at the $\omega$B97X-D/6-311+G(d) level in water (SMD), with $[\ce{X}]=\SI{1}{\mole\per\liter}$.}]{colspec={>{\bfseries}lX[c]X[c]cX[c]X[c]cX[c]X[c]}, width =\linewidth,rowhead=2}
	\hline
	&  \SetCell[c=2]{c} \ce{N+ + A- <=> N+A-} & & & \SetCell[c=2]{c} \ce{N^. + C+ <=> N^.C^+} & & & \SetCell[c=2]{c} \ce{N- + C+ <=> N^-C+}  & \\ 
	\cline{2-3} \cline{5-6} \cline{8-9}
	& $a_{\ce{N+A-}}$ & $\Delta{G}_{cplx}^\star$ &  & $a_{\ce{N^.C+}}$ & $\Delta{G}_{cplx}^\star$ &  & $a_{\ce{N^-C+}}$ & $\Delta{G}_{cplx}^\star$\\
	\hline
1 & 3.95 & 24.1 &  & 5.02 & 19.2 &  & 4.96 & 21.8\\
2 & 3.98 & 19.2 &  & 5.04 & 21.2 &  & 4.96 & 40.1\\
3 & 3.92 & 19.7 &  & 6.05 & 22.8 &  & 4.85 & 39.9\\
4 & 4.12 & 16.1 &  & 5.46 & 21.3 &  & 4.97 & 35.6\\
5 & 5.47 & 16.7 &  & 6.01 & 20.5 &  & 4.90 & 31.2\\
6 & 4.15 & 15.4 &  & 5.42 & 23.3 &  & 4.94 & 38.5\\
7 & 4.92 & 20.2 &  & 6.12 & 24.2 &  & 5.47 & 33.9\\
8 & 4.72 & 20.1 &  & 5.54 & 26.3 &  & 5.24 & 43.2\\
9 & 4.54 & 24.2 &  & 6.13 & 34.2 &  & 5.04 & 49.1\\
10 & 4.91 & 19.2 &  & 5.48 & 31.5 &  & 5.20 & 41.4\\
11 & 4.16 & 8.6 &  & 5.47 & 24.8 &  & 4.93 & 34.0\\
12 & 3.72 & 15.7 &  & 4.99 & 21.6 &  & 4.95 & 29.0\\
13 & 4.28 & 22.2 &  & 5.08 & 20.6 &  & 5.13 & 16.1\\
14 & 3.97 & 20.5 &  & 4.71 & 22.3 &  & 4.65 & 18.5\\
15 & 4.99 & 28.2 &  & 5.14 & 20.3 &  & 5.36 & 15.3\\
16 & 3.95 & 25.9 &  & 5.16 & 28.4 &  & 4.78 & 20.2\\
17 & 5.15 & 18.6 &  & 5.87 & 15.9 &  & 5.24 & 10.0\\
18 & 4.23 & 22.9 &  & 4.94 & 22.3 &  & 4.95 & 26.3\\
19 & 5.39 & 36.7 &  & 5.43 & 35.2 &  & 5.26 & 18.3\\
20 & 4.58 & 56.0 &  & 5.53 & 52.8 &  & 4.90 & 24.2\\
21 & 4.28 & 15.9 &  & 5.34 & 24.3 &  & 5.32 & 15.2\\
22 & 3.94 & 21.6 &  & 4.53 & 22.2 &  & 4.40 & 17.0\\
23 & 4.52 & 20.3 &  & 5.74 & 21.7 &  & 4.78 & 9.6\\
24 & 4.60 & 20.4 &  & 6.75 & 17.8 &  & 4.80 & 7.8\\
25 & 4.24 & 20.5 &  & 6.15 & 17.5 &  & 4.77 & 9.2\\
26 & 4.66 & 24.2 &  & 6.66 & 21.0 &  & 4.67 & 9.5\\
27 & 4.23 & 18.7 &  & 5.88 & 18.4 &  & 4.68 & 10.9\\
28 & 5.19 & 16.7 &  & 7.07 & 18.4 &  & 5.76 & 6.4\\
29 & 4.31 & 18.3 &  & 5.85 & 17.7 &  & 4.79 & 10.4\\
30 & 4.32 & 13.0 &  & 5.92 & 18.9 &  & 4.76 & 7.6\\
31 & 4.63 & 20.4 &  & 6.59 & 20.8 &  & 4.78 & 7.8\\
32 & 4.63 & 21.2 &  & 6.53 & 22.9 &  & 4.76 & 6.0\\
33 & 4.63 & 18.3 &  & 6.58 & 21.4 &  & 5.63 & 18.5\\
34 & 4.71 & 18.3 &  & 6.83 & 15.4 &  & 4.74 & 8.7\\
35 & 4.45 & 12.1 &  & 6.17 & 20.5 &  & 4.69 & 11.7\\
36 & 4.14 & 17.9 &  & 5.71 & 19.2 &  & 4.64 & 6.0\\
37 & 4.56 & 18.6 &  & 6.38 & 18.3 &  & 4.72 & 2.9\\
38 & 5.01 & 17.4 &  & 6.75 & 24.8 &  & 4.99 & -0.7\\
39 & 5.13 & 16.0 &  & 5.59 & 19.4 &  & 7.28 & 18.9\\
40 & 5.20 & 13.5 &  & 7.05 & 26.9 &  & 5.77 & 17.3\\
41 & 5.08 & 19.9 &  & 5.09 & 11.3 &  & 4.98 & 4.7\\
42 & 6.47 & 24.1 &  & 7.25 & 22.8 &  & 4.73 & -4.2\\
43 & 5.61 & 17.8 &  & 6.45 & 18.9 &  & 5.58 & 7.6\\
44 & 5.33 & 17.6 &  & 5.38 & 8.0 &  & 5.40 & 8.2\\
45 & 5.22 & 19.0 &  & 7.27 & 22.0 &  & 5.13 & 8.3\\
46 & 4.97 & 16.0 &  & 7.16 & 26.7 &  & 4.94 & 0.8\\
47 & 5.56 & 16.5 &  & 6.73 & 21.6 &  & 5.55 & 6.2\\
48 & 4.84 & 20.8 &  & 6.10 & 32.5 &  & 4.96 & 16.3\\
49 & 5.54 & 19.3 &  & 4.89 & 13.9 &  & 4.83 & -1.1\\
50 & 4.64 & 19.3 &  & 5.55 & 20.8 &  & 6.53 & 19.1\\
51 & 4.52 & 17.3 &  & 4.83 & 18.3 &  & 4.63 & 6.5\\
52 & 4.12 & 13.2 &  & 4.63 & 9.9 &  & 4.63 & 3.6\\
53 & 4.75 & 15.2 &  & 5.43 & 23.5 &  & 4.64 & 8.6\\
54 & 4.66 & 17.9 &  & 6.22 & 21.0 &  & 4.68 & 0.2\\
55 & 6.10 & 19.0 &  & 6.32 & 18.2 &  & 4.73 & -0.7\\
56 & 5.18 & 17.8 &  & 5.69 & 19.0 &  & 5.56 & -13.3\\
57 & 5.26 & 20.1 &  & 5.96 & 18.4 &  & 4.93 & 5.0\\
58 & 3.95 & 19.4 &  & 5.83 & 18.6 &  & 5.56 & -1.3\\
59 & 4.07 & 20.7 &  & 5.63 & 20.5 &  & 5.73 & 17.9\\
60 & 4.15 & 16.9 &  & 6.08 & 16.1 &  & 4.67 & 11.4\\
61 & 3.77 & 22.2 &  & 5.41 & 23.0 &  & 4.86 & 31.0\\
	\hline
\end{longtblr}

\clearpage
\begin{longtblr}[caption={Radii ($a$, in \si{\angstrom}) of the ion-pair for the 3 oxidation states of the nitroxides, together with their corresponding Gibbs free energy of complexation ($\Delta G^\star_{cplx}$, in \si{\kilo\joule\per\mole}), as computed at the $\omega$B97X-D/6-311+G(d) level in acetonitrile (SMD), with $[\ce{X}]=\SI{1}{\mole\per\liter}$.}]{colspec={>{\bfseries}lX[c]X[c]cX[c]X[c]cX[c]X[c]}, width =\linewidth,rowhead=2}
	\hline
	&  \SetCell[c=2]{c} \ce{N+ + A- <=> N+A-} & & & \SetCell[c=2]{c} \ce{N^. + C+ <=> N^.C^+} & & & \SetCell[c=2]{c} \ce{N- + C+ <=> N^-C+}  & \\ 
	\cline{2-3} \cline{5-6} \cline{8-9}
	& $a_{\ce{N+A-}}$ & $\Delta{G}_{cplx}^\star$ &  & $a_{\ce{N^.C+}}$ & $\Delta{G}_{cplx}^\star$ &  & $a_{\ce{N^-C+}}$ & $\Delta{G}_{cplx}^\star$\\
	\hline
2 & 3.78 & 21.1 &  & 5.09 & 25.3 &  & 4.74 & 16.1\\
3 & 3.78 & 22.3 &  & 6.07 & 30.7 &  & 4.71 & 15.2\\
4 & 3.77 & 19.2 &  & 5.48 & 24.8 &  & 5.24 & 16.0\\
6 & 3.85 & 19.1 &  & ---  & --- &  & 4.90 & 14.0\\
12 & 3.72 & 15.5 &  & 5.03 & 28.4 &  & 4.96 & 2.3\\
15 & 5.08 & 31.2 &  & 5.22 & 24.9 &  & 5.16 & -2.6\\
23 & 4.10 & 25.4 &  & 5.61 & 23.8 &  & 5.56 & -4.8\\
24 & 5.97 & 23.6 &  & 6.63 & 29.3 &  & 6.90 & 3.9\\
25 & 4.32 & 23.4 &  & 6.10 & 24.5 &  & 6.32 & 4.8\\
26 & 6.13 & 26.4 &  & 6.67 & 28.5 &  & 6.90 & 5.5\\
27 & 4.22 & 22.5 &  & 5.80 & 25.8 &  & 6.00 & 4.3\\
33 & 4.65 & 27.2 &  & 6.62 & 30.0 &  & 6.65 & 4.2\\
36 & 4.14 & 21.1 &  & 4.90 & 23.7 &  & 5.80 & -0.3\\
51 & 4.53 & 21.3 &  & 4.97 & 25.9 &  & 6.06 & -1.3\\
54 & 4.63 & 14.0 &  & 5.29 & 27.1 &  & 6.38 & 1.9\\
55 & 4.69 & 17.6 &  & 6.27 & 29.6 &  & 6.38 & 1.3\\
58 & 4.04 & 21.8 &  & 5.86 & 31.1 &  & 5.66 & -17.4\\
59 & 4.09 & 22.4 &  & 5.63 & 30.7 &  & 5.55 & -0.8\\
60 & 4.30 & 24.5 &  & 5.98 & 28.7 &  & 6.20 & 4.1\\
61 & 3.76 & 21.8 &  & 5.49 & 27.9 &  & 4.67 & 17.1\\
	\hline
\end{longtblr}

\begin{figure}[!h]
\centering
\includegraphics [width=\linewidth]{FigureS6}
\caption{Enthalpic ($\Delta H^\star_{cplx}$, filled bars) and entropic (-T$\Delta S^\star_{cplx}$, empty bars)  contributions to the ion-pair formation Gibbs free energy ($\Delta G^\star_{cplx}$, round markers) of the 3 states of the nitroxides, as computed at the $\omega$B97X-D/6-311+G(d) level in water (SMD), with $[\ce{X}]=\SI{1}{\mole\per\liter}$.}
\end{figure}

\clearpage
\begin{longtblr}[caption={Radii ($a$, in \si{\angstrom}) of the ion-pair for the 3 oxidation states of the nitroxides, toghether with their corresponding Gibbs free energy of complexation ($\Delta G^\star_{cplx}$, in \si{\kilo\joule\per\mole}), as computed at the $\omega$B97X-D/6-311+G(d) level in water (SMD), with $[\ce{X}]=\SI{1}{\mole\per\liter}$.}]{colspec={>{\bfseries}lX[c]X[c]cX[c]X[c]cX[c]X[c]}, width =\linewidth,rowhead=2}
	\hline
	&  \SetCell[c=2]{c} \ce{N+ + A- + C+ <=> N+AC} & & & \SetCell[c=2]{c} \ce{N^. + A- + C+ <=> N^.AC} & & & \SetCell[c=2]{c} \ce{N- + A- + C+ <=> N^-AC}  & \\ 
	\cline{2-3} \cline{5-6} \cline{8-9}
	& $a_{\ce{N+AC}}$ & $\Delta{G}_{cplx}^\star$ &  & $a_{\ce{N^.AC}}$ & $\Delta{G}_{cplx}^\star$ &  & $a_{\ce{N^-AC}}$ & $\Delta{G}_{cplx}^\star$\\
	\hline
	1 & 4.77 & 40.4 &  & 4.73 & 43.6 &  & 5.40 & 43.4\\
	2 & 5.28 & 42.9 &  & 4.89 & 42.7 &  & 5.95 & 71.3\\
	3 & 6.31 & 43.5 &  & 5.10 & 40.4 &  & 5.39 & 71.6\\
	4 & 5.67 & 41.5 &  & 6.33 & 45.3 &  & 5.06 & 59.0\\
	5 & 6.24 & 42.7 &  & 6.70 & 47.2 &  & 4.90 & 58.1\\
	6 & 5.31 & 40.0 &  & 6.52 & 44.1 &  & 5.10 & 60.7\\
	7 & 6.11 & 41.6 &  & 5.57 & 42.4 &  & 5.50 & 63.5\\
	8 & 6.02 & 43.2 &  & 4.87 & 36.0 &  & 5.38 & 63.3\\
	9 & 5.51 & 39.3 &  & 5.47 & 43.9 &  & 6.82 & 74.0\\
	10 & 5.40 & 37.5 &  & 5.13 & 39.0 &  & 5.90 & 63.6\\
	11 & 6.08 & 37.7 &  & 6.34 & 34.1 &  & 5.18 & 54.4\\
	12 & 5.38 & 44.0 &  & 4.73 & 40.0 &  & 4.88 & 54.4\\
	13 & 5.26 & 43.5 &  & 4.99 & 38.4 &  & 5.05 & 41.0\\
	14 & 5.41 & 45.4 &  & 4.67 & 44.7 &  & 4.96 & 46.9\\
	15 & 5.10 & 44.7 &  & 5.36 & 55.6 &  & 5.65 & 46.6\\
	16 & 4.97 & 43.5 &  & 6.04 & 50.9 &  & 5.97 & 52.4\\
	17 & 5.51 & 43.5 &  & 5.51 & 43.5 &  & 5.10 & 49.5\\
	18 & 4.92 & 42.0 &  & 4.99 & 37.7 &  & 6.65 & 52.4\\
	19 & 5.30 & 52.8 &  & 5.36 & 59.5 &  & 6.68 & 47.0\\
	20 & 6.62 & 74.4 &  & 5.36 & 72.4 &  & 5.71 & 54.6\\
	21 & 4.68 & 43.3 &  & 4.54 & 33.9 &  & 5.14 & 36.0\\
	22 & 4.71 & 41.2 &  & 4.61 & 47.1 &  & 4.87 & 43.4\\
	23 & 4.98 & 38.3 &  & 5.66 & 44.3 &  & 6.01 & 46.7\\
	24 & 6.57 & 39.7 &  & 6.80 & 39.8 &  & 6.56 & 45.1\\
	25 & 6.21 & 34.4 &  & 5.44 & 39.2 &  & 6.19 & 44.1\\
	26 & 6.10 & 37.8 &  & 5.94 & 43.7 &  & 6.74 & 43.5\\
	27 & 6.21 & 35.1 &  & 5.24 & 40.1 &  & 5.89 & 39.2\\
	28 & 6.51 & 27.6 &  & 7.11 & 37.9 &  & 7.09 & 37.3\\
	29 & 5.27 & 30.9 &  & 6.55 & 39.4 &  & 6.43 & 51.6\\
	30 & 5.23 & 28.4 &  & 6.17 & 39.3 &  & 5.15 & 38.3\\
	31 & 6.50 & 37.8 &  & 5.92 & 34.4 &  & 6.13 & 40.1\\
	32 & 5.55 & 34.3 &  & 6.02 & 40.0 &  & 6.63 & 43.9\\
	33 & 6.52 & 37.3 &  & 6.68 & 44.8 &  & 6.47 & 37.9\\
	34 & 6.26 & 32.6 &  & 6.21 & 36.3 &  & 6.88 & 44.3\\
	35 & 5.33 & 33.3 &  & 5.28 & 34.3 &  & 6.26 & 33.8\\
	36 & 5.00 & 24.4 &  & 5.75 & 38.3 &  & 5.24 & 37.0\\
	37 & 5.30 & 35.0 &  & 5.70 & 37.4 &  & 6.51 & 34.2\\
	38 & 5.26 & 22.3 &  & 6.31 & 46.8 &  & 6.45 & 37.8\\
	39 & 5.24 & 22.1 &  & 5.98 & 40.5 &  & 5.94 & 34.9\\
	40 & 6.66 & 32.8 &  & 6.81 & 45.4 &  & 6.59 & 52.2\\
	41 & 6.36 & 35.3 &  & 7.20 & 40.1 &  & 5.62 & 38.0\\
	42 & 5.20 & 23.9 &  & 7.08 & 45.3 &  & 7.43 & 37.9\\
	43 & 5.88 & 31.4 &  & 5.97 & 35.7 &  & 5.63 & 38.1\\
	44 & --- & --- &  & 6.08 & 28.6 &  & --- & ---\\
	45 & 5.16 & 19.4 &  & 6.97 & 42.6 &  & 7.17 & 47.7\\
	46 & 5.18 & 25.1 &  & 7.11 & 54.7 &  & 7.22 & 47.8\\
	47 & 5.56 & 22.2 &  & 6.86 & 39.4 &  & 6.46 & 27.1\\
	48 & 5.76 & 37.6 &  & 6.06 & 34.4 &  & 6.15 & 31.3\\
	49 & 5.01 & 33.3 &  & 5.11 & 36.2 &  & 5.55 & 32.8\\
	50 & 5.88 & 39.9 &  & 6.53 & 39.6 &  & 6.27 & 40.7\\
	51 & 4.97 & 20.4 &  & 5.45 & 36.0 &  & 5.22 & 37.6\\
	52 & 5.60 & 29.7 &  & 5.37 & 34.7 &  & 5.16 & 34.1\\
	53 & 5.01 & 19.1 &  & 5.29 & 37.8 &  & 5.33 & 40.8\\
	54 & 5.14 & 34.4 &  & 5.83 & 35.6 &  & 5.67 & 37.4\\
	55 & 5.11 & 24.2 &  & 5.97 & 23.9 &  & 5.87 & 31.7\\
	56 & 5.79 & 38.7 &  & 5.61 & 44.5 &  & 6.60 & 16.0\\
	57 & 5.90 & 44.6 &  & 4.67 & 32.6 &  & 5.72 & 34.0\\
	58 & 6.36 & 42.0 &  & 6.53 & 40.3 &  & 6.46 & 23.8\\
	59 & 6.31 & 47.3 &  & 6.59 & 44.0 &  & 6.61 & 41.5\\
	60 & 6.33 & 33.2 &  & 6.42 & 41.4 &  & 6.19 & 43.4\\
	61 & 5.57 & 47.1 &  & 5.89 & 40.9 &  & 5.03 & 72.7\\
	\hline
\end{longtblr}

\clearpage
\begin{longtblr}[caption={Radii ($a$, in \si{\angstrom}) of the ion-pair for the 3 oxidation states of the nitroxides, toghether with their corresponding Gibbs free energy of complexation ($\Delta G^\star_{cplx}$, in \si{\kilo\joule\per\mole}), as computed at the $\omega$B97X-D/6-311+G(d) level in acetonitrile (SMD), with $[\ce{X}]=\SI{1}{\mole\per\liter}$.}]{colspec={>{\bfseries}lX[c]X[c]cX[c]X[c]cX[c]X[c]}, width =\linewidth,rowhead=2}
	\hline
	&  \SetCell[c=2]{c} \ce{N+ + A- + C+ <=> N+AC} & & & \SetCell[c=2]{c} \ce{N^. + A- + C+ <=> N^.AC} & & & \SetCell[c=2]{c} \ce{N- + A- + C+ <=> N^-AC}  & \\ 
	\cline{2-3} \cline{5-6} \cline{8-9}
	& $a_{\ce{N+AC}}$ & $\Delta{G}_{cplx}^\star$ &  & $a_{\ce{N^.AC}}$ & $\Delta{G}_{cplx}^\star$ &  & $a_{\ce{N^-AC}}$ & $\Delta{G}_{cplx}^\star$\\
	\hline
2 & 5.55 & 56.3 &  & 6.09 & 53.9 &  & 5.85 & 54.2\\
3 & 6.35 & 57.7 &  & 6.06 & 59.2 &  & 5.49 & 57.1\\
4 & 5.94 & 58.0 &  & 6.36 & 55.9 &  & 6.57 & 48.4\\
6 & 5.32 & 56.1 &  & 4.73 & 41.5 &  & 5.16 & 48.6\\
12 & 5.71 & 57.1 &  & 4.90 & 47.9 &  & 4.95 & 34.3\\
15 & 6.42 & 66.2 &  & 5.25 & 61.9 &  & 6.26 & 28.9\\
23 & 6.25 & 54.7 &  & 5.64 & 47.4 &  & 5.51 & 30.7\\
24 & 6.53 & 55.9 &  & 6.74 & 58.2 &  & 6.60 & 39.2\\
25 & 6.63 & 58.2 &  & 5.58 & 51.1 &  & 6.27 & 34.7\\
26 & 6.16 & 51.3 &  & 6.08 & 53.8 &  & 6.87 & 34.0\\
27 & 6.19 & 50.7 &  & 5.90 & 58.2 &  & 5.93 & 33.4\\
33 & 6.40 & 58.9 &  & 6.22 & 54.6 &  & 6.55 & 36.9\\
36 & 6.09 & 49.8 &  & 6.36 & 51.2 &  & 5.66 & 30.2\\
51 & 5.17 & 44.6 &  & 6.22 & 52.6 &  & 6.74 & 29.8\\
54 & 5.19 & 37.3 &  & 6.24 & 52.2 &  & 6.74 & 39.0\\
55 & 5.11 & 39.5 &  & 6.23 & 47.7 &  & 6.85 & 34.7\\
58 & 6.16 & 60.1 &  & 6.62 & 47.0 &  & 6.47 & 7.7\\
59 & 6.23 & 58.6 &  & 6.65 & 53.0 &  & 6.49 & 35.4\\
60 & 6.23 & 50.1 &  & 6.41 & 57.1 &  & 6.15 & 31.4\\
61 & 6.41 & 59.2 &  & 5.83 & 54.6 &  & 5.24 & 49.4\\
	\hline
\end{longtblr}

\clearpage
\begin{longtblr}[caption={Litterature experimental $E^0_{rel}(\ce{N+}|\ce{N^.})$ (in \si{\milli\volt} vs SHE), measured in water and acetonitrile. When two values are reported, the first one is used in the regressions and discussions.},
		note{a} = {From Ref.~\citenum{goldsteinStructureActivityRelationship2006}.},
		note{b} = {From Ref.~\citenum{morrisChemicalElectrochemicalReduction1991}, converted from SCE to SHE with +\SI{244}{\milli\volt} \cite{pavlishchukConversionConstantsRedox2000}.},
		note{c}={From Ref.~\citenum{blincoExperimentalTheoreticalStudies2008}.},
		note{d}={From Ref.~\citenum{zhangEffectHeteroatomFunctionality2018}, converted from Fc to SHE with +\SI{624}{\milli\volt} \cite{pavlishchukConversionConstantsRedox2000}.},
		label={tab:exp}
	]{colspec={>{\bfseries}lX[c]X[c]c>{\bfseries}lX[c]X[c]}, width = 0.85\linewidth,rowhead=1}
	\hline
	& Water & Acetonitrile  & & & Water & Acetonitrile\\
	\hline
		2 & 740\TblrNote{a} & 850\TblrNote{c}, 858\TblrNote{d} &  & 33 & --- & 1123\TblrNote{c} \\
		3 & 805\TblrNote{a}, 774\TblrNote{b} & 924\TblrNote{c}, 939\TblrNote{d} &  & 36 & --- & 1010\TblrNote{c} \\
		4 & 817\TblrNote{a}, 874\TblrNote{b} & 1063\TblrNote{c} &  & 51 & --- & 1102\TblrNote{c} \\
		6 & 825\TblrNote{a}, 724\TblrNote{b} & 877\TblrNote{c}, 908\TblrNote{d} &  & 54 & --- & 1096\TblrNote{c} \\
		11 & 892\TblrNote{a} & --- &  & 55 & --- & 1175\TblrNote{c} \\
		12 & 918\TblrNote{a}, 914\TblrNote{b} & 1034\TblrNote{d} &  & 56 & 867\TblrNote{a}, 874\TblrNote{b} & --- \\
		13 & 795\TblrNote{a} & --- &  & 57 & 853\TblrNote{a} & --- \\
		15 & 870\TblrNote{a}, 784\TblrNote{b} & 976\TblrNote{c} &  & 58 & 955\TblrNote{a}, 974\TblrNote{b} & 1073\TblrNote{d} \\
		18 & 814\TblrNote{b} & --- &  & 59 & --- & 1109\TblrNote{d} \\
		23 & --- & 1045\TblrNote{c} &  & 60 & --- & 1099\TblrNote{c} \\
		24 & --- & 1095\TblrNote{c} &  & 61 & --- & 996\TblrNote{d} \\
		25 & --- & 990\TblrNote{c} &   \\
		26 & --- & 1030\TblrNote{c} & \\
		27 & --- & 1023\TblrNote{c} &  &  &  &  \\
	\hline
\end{longtblr}

\begin{figure}[!h]
	\centering
	\includegraphics[width=.75\linewidth]{FigureS7}
	\caption{Comparison between experimental ($E^0_{rel} $ vs SHE, from Table \ref{tab:exp}) and calculated relative oxidation potential ($E^f_{rel}$ vs SHE) in water (top) and acetonitrile (bottom)  as computed at the $\omega$B97X-D/6-311+G(d) level  using SMD, but \textbf{without} correction due to DH or ion-pair formation.  The dashed line is a linear regression.}
	\label{fig:expvstheo}
\end{figure}

\clearpage



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