# Oxidative Addition of Nitro-Perylenediimide onto Palladium(0): A theoretical and experimental study

Jules Schleinitz, Clara Chinchilla-Garzon, Anna Perfetto, Emile Escoudé, Aline Makhloutah, Geoffrey Gontard, Maxime Vitale, Antoine Goujon, François-Xavier Felpin, Laurent Binet, et al.

► To cite this version:

Jules Schleinitz, Clara Chinchilla-Garzon, Anna Perfetto, Emile Escoudé, Aline Makhloutah, et al. "Oxidative Addition of Nitro-Perylenediimide onto Palladium(0): A theoretical and experimental study." Organometallics, 2024, 44 (1), pp.29-35. 10.1021/acs.organomet.4c00326. hal-05349569

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# Oxidative Addition of Nitro-Perylenediimide onto Palladium(0):
A theoretical and experimental study

Jules Schleinitz,ª Clara Chinchilla-Garzon,ab,ª Anna Perfetto,ᵇ Emile Escoudé,ª Aline Makhloutah,ᶜ Geof-
frey Gontard,ᵈ Maxime R. Vitale,ª Antoine Goujon,ᶜ François-Xavier Felpin,ᵉ Laurent Binet,f Ilaria
Ciofini,*,b Piétrick Hudhomme,*,c Laurence Grimaud.*a

**ABSTRACT:** Palladium-catalyzed cross-coupling reactions, particularly the Suzuki-Miyaura coupling, are efficient tools for constructing C-C bonds due to their exceptional versatility and efficiency. Recently, nitroarenes have been explored as new electrophilic substrates in palladium-catalyzed denitrative Suzuki-Miyaura coupling, offering an alternative to the traditionally used organic halides or triflates. The oxidative addition of nitro derivatives onto palladium catalysts remains challenging and often requires harsh conditions and expensive catalytic systems. Nevertheless, we recently demonstrated that nitro-perylenediimide derivatives can effectively engage in various cross-couplings with unsophisticated Pd(PPh₃)₄ as catalytic system. The mechanistic study of the oxidative addition step for this particular class of nitro-derivatives revealed an unprecedented single electron transfer event, which is supported by a comprehensive range of analyses including NMR, X-Ray diffraction, HRMS and EPR experiments, complemented with cyclic voltammetry and theoretical calculations.

**Oxidative Addition via a SET**

<figure><img src="image_2.png" /></figure>

## INTRODUCTION

Perylenediimide (PDI) derivatives continue to be extensively developed as electron acceptors in organic electronics,¹,²,³,⁴ and more recently, as fluorescent dyes for biological or medicinal applications,⁵,⁶,⁷ due to their exceptional chemical, thermal and photochemical stability, along with their particularly interesting photophysical properties. While the functionalization of the PDI backbone has mainly used PDI derivatives substituted by one or more halogen atoms in the *bay* positions as starting materials,⁸ the recent introduction of nitro groups has sparked interest as new building blocks.⁹ In addition to the use of the nitro group as a leaving group in aromatic nucleophilic substitutions,¹⁰ the possibility of considering organometallic couplings on these nitroarenes is highly appealing. Cross-coupling reactions of nitroarenes have attracted much attention and Rh-, Cu- or Pd-catalyzed cross-couplings have been reported, but most of them are limited to very electron-poor nitroarenes.¹¹,¹²,¹³,¹⁴

The synthesis of diaryl ethers derivatives by denitrative coupling of nitroarenes with aryl boronic acids has been reported using a 2,2'-bipyridine palladacycle catalyst.¹⁵ Other approaches of palladium-catalyzed denitrative couplings have been developed to achieve the synthesis of unsymmetrical diaryl ethers from either arylboronic acids¹⁶ or phenols,¹⁷ and sulfinates from sulfones.¹⁸ All these couplings proceeded with electron-deficient nitroarenes using low catalyst loadings under basic conditions at high temperature. A significant breakthrough was made using the Pd/BrettPhos catalytic system to perform efficient Suzuki-Miyaura coupling (SMC) reaction with a broader scope of nitroarenes.¹⁹,²⁰,²¹,²² As a main drawback, the reaction requires harsh conditions (c.a. 130 °C) with an expensive catalytic system using the BrettPhos ligand. This Pd/BrettPhos catalytic system has been later involved in various denitrative couplings such as Buchwald-Hartwig amination,²³ reduction,²⁴ intramolecular arylation,²⁵ Sonogashira-type alkynylation,²⁶ Mizoroki-Heck-type

<footnote>a Laboratoire de Biomolécules (LBM), Département de Chimie, Sorbonne Université, École Normale Supérieure, PSL University, Sorbonne Université, CNRS, 75005 Paris, France.</footnote>

<footnote>b Chimie Paris Tech, PSL University, CNRS, Institute of Chemistry for Life and Health Sciences, 75005 Paris, France.</footnote>

<footnote>c Univ Angers, CNRS, MOLTECH-Anjou, SFR Matrix, 49045 ANGERS, France.</footnote>

<footnote>d Sorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, 75005, Paris, France.</footnote>

<footnote>e Nantes Université, CNRS, CEISAM UMR 6230, F-44000 Nantes, France.</footnote>

<footnote>f ChimieParisTech-PSL, PSL University, CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France.</footnote>
alkenylation,²⁷ methylation,²⁸ α-arylation of ketones,²⁹ and more recently Stille-type coupling³⁰ and aryl cyanation.³¹ An enhancement in the Pd catalytic activity was noted by substituting the BrettPhos ligand with imidazo[1,5-a]pyridinylidene ligands, renowned for emulating Buchwald-type biaryl phosphines. N-heterocyclic carbene ligands are believed to exhibit lower susceptibility to oxidation compared to phosphines, particularly in the presence of nitrates at elevated temperatures.³²,³³ Regarding the use of nitroarenes as electrophiles in SMC reaction, Nakao and coll. demonstrated that oxidative addition constitutes the rate-limiting step for the Pd/BrettPhos-catalyzed process and that a pre-coordination of the nitro aryl derivative occurs prior to the formation of the aryl palladium complex.²⁰ The reaction with 1-nitronaphthalene afforded the corresponding η²-Pd(0) complex whose structure was confirmed by X-ray crystallography. Although the latter was shown to be unstable, theoretical calculations suggested that it might be involved in the oxidative addition process.

We reported the first SMC reaction between a nitro-PDI derivative and a boronic acid, proceeding in high yields with Pd(PPh₃)₄ as catalyst, without any additional expensive ligand.³⁴ These reaction conditions proved to be successful for a wide variety of boronic esters, leading to the synthesis of PDI dimers, trimers, and tetramers.³⁵ Finally, we highlighted the major advantage of the nitro group by carrying out the reaction using a dinitro-PDI derivative. The reaction showed remarkable selectivity, allowing the control of mono-substitution by offering desymmetrization possibilities in the bay region of the PDI unit.³⁶ Intrigued by the efficiency of this denitrative SMC which can be achieved on nitro-PDI compounds without the requirement of an expensive phosphine, we present here our investigations on the mechanism of the oxidative addition, combining both experimental and theoretical studies.

## RESULTS AND DISCUSSION

Palladium-catalyzed SMC with mononitro-PDI (PDI-NO₂) derivatives proceed in the presence of Pd(PPh₃)₄ as catalyst, potassium phosphate or potassium carbonate as base, in THF or a mixture of THF/H₂O in 9/1 ratio at 75 °C. In these conditions, the expected coupling products are obtained in 75-85% yields (Scheme 1).³⁴,³⁵,³⁷ It is important to note that the addition of Pd(PPh₃)₄ catalyst in the reaction mixture, at room temperature, results almost immediately in a color change from red to red-brown.

<figure><img src="image_3.png" /><figcaption>**Scheme 1.** Suzuki-Miyaura coupling reaction using PDI-NO₂ derivatives.</figcaption></figure>

For this study, the mononitro-PDI derivative **1** bearing cyclohexyl (Cy) groups at the imide positions was chosen as

the model substrate, because of its propensity to afford crystal-line compounds. The oxidative addition complex Pd(PDI)(NO₂)(PPh₃)₂ **2** was prepared under stoichiometric conditions of PDI-NO₂ **1** and PdCp(allyl) in THF in the presence of three equivalents of triphenylphosphine (Figure 1a). After dilution with diethyl ether, the complex **2** was precipitated as a red powder (S.I., Section I.2 for details). The ³¹P{¹H} NMR spectrum in THF-d8 displays two broad singlets at 17.5 and 20.8 ppm respectively which, in accord with two species in equilibrium, collapsed when the temperature was gradually increased (Figure 1c). We hypothesized that this could be related to the partial ionization of the complex due to the weak coordination of the nitrite counter-anion to the Pd. This was further corroborated by the fact that in a less polar solvent such as toluene, there is only one peak on the ³¹P{¹H} NMR spectrum (Figure S19). Moreover, the addition of tetra-*n*-butylammonium chloride (TBACl) resulted in only one signal at 22.9 ppm attributed to the Pd(PDI)Cl(PPh₃)₂ (S.I. Section I.2.c and Figure S24). The structure of the latter was further confirmed by X-Ray diffraction (XRD) analysis (Figure S34). The oxidative addition complex **2** was finally crystallized by diffusion of pentane in chloroform solution and the structure of *N*-ligated Pd-complex was confirmed by XRD analysis (Figure 1a, S.I. Section I.2.e). The cyclic voltammetry (CV) of complex **2** displays two reduction peaks $E_p^{1red} = -0.70$ V and $E_p^{2red} = -1.20$ V versus Ag/AgCl (KCl 3M) (red curve in Figure 1b) corresponding to the successive formation of radical anion PDI• and dianion PDI²⁻ species. These values are significantly shifted to more negative values compared to those of PDI-NO₂ **1** which is characterized by two reduction peaks at $E_p^{1red} = -0.32$ V and $E_p^{2red} = -0.60$ V versus Ag/AgCl (KCl 3M).

The oxidative addition of PDI-NO₂ **1** with Pd(PPh₃)₄ was monitored in THF-d8 by ³¹P{¹H} NMR at room temperature following the formation of the two characteristic signals of complex **2** (Figure 1d). A color change was detected just after mixing both, and when reaching completion, after approximately 3 hours, we observed the appearance of the free triphenylphosphine by ³¹P{¹H} NMR. The oxidative addition of PDI-NO₂ **3** (R' = CH(*n*-hexyl)₂) with Pd(PPh₃)₄ in THF at 50 °C was also followed by high-resolution electrospray ionization mass spectrometry. Two Pd-containing species were observed at *m/z* = 1385.5458 and *m/z* = 1424.5679 attributed to Pd(PDI)(PPh₃)₂⁺ and Pd(PDI)(PPh₃)₂(CH₃CN)⁺, respectively (S.I., Figure S35, the CH₃CN ligand originates from the dilution solvent for HRMS analysis). This result confirms the observations made for the oxidative addition of Pd(PPh₃)₄ to PDI **1**. The identified cationic complexes also suggest the lability of the Pd-NO₂ bond. Theoretical studies performed at the Density Functional Theory (DFT) level allowed us to estimate the reaction pathway and the associated activation energy. Of note we consider here, among the possible specification present in solution, only Pd(PPh₃)₂. As expected, the rate-determining step for the formation of the oxidative addition complex is breaking the C-N bond (43.1 kcal mol⁻¹), as reported in Figure 2a in the case of nitrobenzene. The successive isomerization of the nitro group on the Pd coordination sphere is practically barrierless (1.7 kcal mol⁻¹). Furthermore, this second barrier is not expected to be strongly dependent on the nature of the nitroaryl considered. The activation energy computed in the case of PDI (18.7 kcal mol⁻¹) is significantly lower compared to that computed at the same level of theory for
nitrobenzene (43.1 kcal mol⁻¹) or the barrier reported by the Nakao and coll. for the oxidative addition of the para-methoxy nitrobenzene using the Pd/BrettPhos catalytic system (29.6 kcal mol⁻¹).²⁰,²¹ The oxidative addition step has been next systematically studied for selected nitroarenes compounds (nitrobenzene, 1-nitropyrene, 4-nitrophthalimide, and PDI-NO₂). The computed ΔE° (reported in S.I., Section IV, Figure S43 and Table S3) are consistent with the experimental findings. In particular, the high barriers computed for all reactants but PDI-NO₂, is consistent with their observed absence of reactivity. More precisely, barriers, computed with respect to the energy of the precomplex, of 42.0 kcal mol⁻¹ (nitrobenzene), 33.9 kcal mol⁻¹ (1-nitropyrene), 30.9 kcal mol⁻¹ (4-nitrophthalimide), 29.8 kcal mol⁻¹ (1,4-dinitrobenzene), and 18.7 kcal mol⁻¹ (PDI-NO₂) were computed (Table S3). These data also show how the reaction seems somehow modulated

by the presence of a secondary electron-withdrawing group (EWG) (ex. 1,4-dinitrobenzene) or a more extended π-system. However, even in the case of PDI-NO₂, the computed barrier (18.7 kcal mol⁻¹) is still high to account for a reaction occurring at room temperature especially when considering that in this case the formation of adduct I is disfavored by roughly 9 kcal mol⁻¹ (Figure 2b).

We noticed that the integration for all the signals on the ³¹P{¹H} NMR spectrum is not constant over time and a large portion of the mass balance based on ³¹P NMR signals is missing for the first hour. We hypothesized that this could be the result of a fast-relaxing system due to the presence of radicals. To assess this hypothesis, we resorted to Electron Paramagnetic Resonance (EPR) measurements (S.I., Section V).

<figure><img src="image_4.png" /><figcaption>**Figure 1.** a) Oxidative addition of PDI-NO₂ **1** and X-Ray analyses of complex **2**; b) Cyclic voltammograms of isolated complex **2** (red color) and the mixture of PDI-NO₂ **1** and complex **2** (blue color) in a THF solution containing 0.1 M of *n*Bu₄NBF₄ with a glassy carbon (*d* = 1 mm) as working electrode and Ag/AgCl (KCl 3M in H₂O) as reference electrode at a scan rate of 0.1 V s⁻¹; c) ³¹P{¹H} NMR of complex **2** and evolution with increasing temperature; d) Kinetic monitoring of the oxidative addition by ³¹P{¹H} NMR following the signals of complex **2** (blue dots), the one of released PPh₃ (red dots) and the sum of all phosphorous derivatives (black dots); e) EPR spectra of a stoichiometric mixture of PDI-NO₂ **1** and Pd(PPh₃)₄ in THF at room temperature (experimental in black and simulated in red, refer to S.I. for details).</figcaption></figure>
<figure><img src="image_5.png" /></figure>

**Figure 2.** Reaction energy profile (in kcal mol⁻¹) computed in THF for the oxidative addition of nitrobenzene (left); and of PDI-NO₂ (substituted with isopropyl groups at the imide positions for simplification) (right). Refer to S.I. for computational details. Activation energies were computed with respect to a pre-complex formed from Pd(PPh₃)₂ and Aryl-NO₂ although different speciation of Pd(PPh₃)₄ may be envisaged in solution. Indeed, this assumption is not expected to alter the conclusion drawn on the relative reactivity of the nitroarenes considered (see text).

When mixing both Pd(PPh₃)₄ and PDI-NO₂ **1** in THF under stoichiometric conditions, an EPR signal at *g* = 2.0035 ± 0.0002 for the radical anion **1**⁻ was detected (Figure 1e). PDI-derived radical anions were indeed previously characterized and shown to be very stable.³⁸,³⁹ The *g*-tensor of the radical anion **1**⁻ computed at the DFT level using the PBE0 and the tailored EPR-II basis set (see S.I., Section IV.3 for details) predicts a shift from the free electron value of Δ*g*<sub>xx</sub> = 65.8, Δ*g*<sub>yy</sub> = 1811.0, Δ*g*<sub>zz</sub> = 2220 ppm corresponding to a *g*<sub>iso</sub> of 2.0036, in excellent agreement with experimentally observed *g*-value. This *g*-tensor close to free electron value also reflects how the radical anion is largely delocalized over the aromatic system, as can be easily remarked by the analysis of the computed spin density reported in S.I. The simulation of the EPR spectra was performed including the ¹H and ¹⁴N nuclei whose DFT predicted hyperfine constants are larger than the experimental linewidth (that is ca. 0.28 MHz). Although a systematic scaling of 0.74 has been applied to DFT hyperfine constants values, the remarkable agreement between simulated and the experimental spectra shows the excellent correlation of experimental and computed hyperfine constants. Therefore, these EPR data show that the species present can be uniquely identified as the radical anion **1**⁻. It is well known that nitroarenes acting as electron acceptors in the presence of nucleophiles can generate nitroaromatic anion radicals that can be detected by EPR.⁴⁰ It suggests that the mechanism could take place via a two steps process: first, a Single Electron Transfer (SET), followed by a radical-anion / radical coupling.⁴¹ This result led us to conclude that the oxidative addition proceeds through a SET mechanism, a finding further confirmed by DFT calculations of redox properties as reported in table S4. This SET is consistent with the very high reduction potential (*E*<sub>p</sub><sup>1red</sup> = -0.32 V vs Ag/AgCl (KCl 3M)) measured by CV of PDI-NO₂ **1** in THF. Considering the oxidation potential of Pd(PPh₃)₄ (*E*<sub>p</sub><sup>ox</sup> ≈ + 0.4 V vs Ag/AgCl)⁴² this SET could proceed either inner or outer sphere.

With the hope to expand the scope of the reaction beyond the PDI core, we investigated a set of nitroaromatic compounds with π-extended systems that should be suitable for the Nakao

pre-complex and be easily reducible. Unfortunately, prediction performed at the DFT level shows that the high reductive potential of PDI-NO₂ was not approached by any of the common nitro derivatives tested (Figure S43, Table S2). Indeed, all the tested π-extended systems as large as nitropyrene failed to undergo an oxidative addition in THF at moderate temperature (see S.I. Section IV.2. for further details). Finally, we investigated the oxidative addition of PDI-X derivatives bearing different substituents in bay position varying the X group (Scheme 2). For this purpose, the 2-hexylheptyl chain was introduced in the imide position to increase the solubility of the PDI derivatives. Worthy of note, functionalization at this imide position does not significantly affect the optical and electronic properties of the PDIs, since the nitrogen of the imide functionality is a node in the π-conjugation of PDI.⁴³⁻⁴⁵ Consequently, the phenoxy (PDI-OPh **4**) and methoxy (PDI-OMe **5**) groups were introduced by nucleophilic substitution onto PDI-NO₂ **3** using K₂CO₃ as a base in 85% and 74% yields, respectively (S.I. Section I.1 for synthetic details).⁴⁶ A modified Sandmeyer reaction was used from PDI-Br **6**⁴⁷ as starting material to reach cyano (PDI-CN **7**) and chloro (PDI-Cl **8**) derivatives in 83% and 36% yields, respectively ((S.I. Section I.1)).⁴⁸ The reduction potential of each PDI derivative was determined by CV (Table S1, Figures S37-S42).

In parallel, the mixture of each PDI compound with Pd(PPh₃)₄ in THF was analyzed by EPR at room temperature (S.I. Section V.2). The PDI-OMe and PDI-OPh remained unchanged and EPR remained silent (Figures S46-S47). If no signal could be detected with PDI-Br (Figure S48), the Pd(PDI)Br(PPh₃)₂ formation could be attested by ³¹P{¹H} NMR, consistently with either a very rapid SET-recombination of the corresponding radicals, or a concerted pathway for the oxidative addition (S.I., Section I.2.d). Interestingly, the characteristic signal of radical anion of PDI could be detected by EPR when using PDI-Cl (Figure S49) and PDI-CN (Figure S50). The former undergoes oxidative addition as evidenced by a characteristic ³¹P{¹H} NMR signal at 22.48 ppm. However, no oxidative addition could be observed with PDI-CN.
<figure><img src="image_6.png" /><figcaption>**Scheme 2.** PDI derivatives with different substituents (X) in the bay region and their positive (v) or negative (x) response to Pd(PPh₃). In parentheses is given the *E*<sub>p</sub><sup>1red</sup> of the substituted PDIs recorded by cyclic voltammetry (vs Ag/AgCl) in solution at C = 10⁻³ mol L⁻¹ in 0.1 M Bu₄NBF₄/THF on GC (3 mm), scan rate = 100 mV/s.</figcaption></figure>

CONCLUSION

Denititative cross-coupling reactions of nitroarenes are classi-
cally developed using the Pd/BrettPhos catalytic system. An
improved system has been demonstrated in the
perylenediimide (PDI) series where Suzuki-Miyaura coupling
(SMC) is an attractive alternative to the use of PDI-Br deriva-
tives. The efficiency of the method using Pd(PPh₃)₄ as a sim-
ple catalyst in mild conditions without any additional ligand is
the result of a peculiar mechanism. The experimental results
led us to propose that the oxidative addition proceeds accord-
ing to a Single Electron Transfer (SET) mechanism, which is
still, to the best of our knowledge, unprecedented for palladi-
um-catalyzed cross-coupling reactions.

EXPERIMENTAL SECTION

**General Methods.** All reactions were carried out under argon atmosphere using standard Schlenk techniques in either oven dried or flame dried glassware, unless otherwise mentioned.

Synthetic Procedure for Pd(PDI)(NO₂)(PPh₃)₂ 2. In a 50 mL Schlenk tube previously flame dried and connected to a Schlenk line was added PDI-NO₂ 1 (240 mg, 0.40 mmol, 1 equiv.), triphenylphosphine (315 mg, 1.2 mmol, 3.0 equiv.) and PdCpAllyl (85 mg, 0.40 mmol, 1.0 equiv.). The solids were put under argon by doing 3 vacuum-argon cycles and degassed THF (24 mL, dried over sodium). The mixture was stirred during 2 h at 50 °C then approximately half of the solvent was removed under vacuum using the Schlenk line. Diethyl ether (20 mL) was then added under stirring and the solution was cooled with an ice bath to crystallize most of the complex. The supernatant was then removed by cannula-filtration and the solid was washed with diethyl ether and dried under vacuum. Complex 2 was isolated as a red powder (346 mg, 70%). Crystallization by liquid or gas diffusion of pentane into a concentrated chloroform solution of the complex afforded crystals suitable for X-ray diffraction analysis.

Cyclic Voltammetry. All the cyclic voltammograms were obtained using a Metrohm potentiostat PGSTAT 100N with a 2 mM solu- tion of the analyte in degassed THF under argon atmosphere (5 mL), using tetrabutylammonium tetrafluoroborate (TBABF₄) (0.1 M) as the supporting electrolyte. The working electrode was a 3 mm glassy carbon, the counter electrode was a Pt wire and the reference electrode a Ag/AgCl with an aqueous KCl solution

(3M). The ohmic drop was compensated. For each PDI-X studied,
a cyclic voltammetry was performed at a scan rate of 0.1 V s⁻¹.

**EPR Measurements.** The EPR spectra were recorded at room temperature with a Bruker Elexsys E500 spectrometer operating at X-band (microwave frequency *ca.* 9.845 GHz) and equipped with a Bruker SHQE resonator. The magnetic field was modulated at 100 kHz with an amplitude 0.005 mT for lock-in detection. The spectrum of PDI-NO₂ + Pd(PPh₃)₄ was recorded with a microwave power 20 mW and the spectra of the other samples with a power 2 mW.

CONTENT

Supporting Information

The Supporting Information is available free of charge on the
ACS Publications website.

Synthetic procedures, ¹H, ¹³C, ³¹P spectra, HRMS spectra, cyclic voltammograms, X-ray analyses of Pd(PDI)(NO₂)(PPh₃)₂ and Pd(PDI)Cl(PPh₃)₂ complexes, DFT calculations details, EPR spectra and xyz file.

AUTHOR INFORMATION

Corresponding *Authors*

**Laurence Grimaud** - Laboratoire de Biomolécules (LBM), Département de Chimie, Sorbonne Université, École Normale Supérieure, PSL University, Sorbonne Université, CNRS, 75005 Paris, France. [orcid.org/0000-0003-3904-1822](https://orcid.org/0000-0003-3904-1822).

Email: [laurence.grimaud@ens.psl.eu](mailto:laurence.grimaud@ens.psl.eu)

**Piétrick Hudhomme** – Univ Angers, CNRS, MOLTECH-Anjou, SFR Matrix, 49045 ANGERS, France. [orcid.org/0000-0002-7383-9603](https://orcid.org/0000-0002-7383-9603)

Email: [pietrick.hudhomme@univ-angers.fr](mailto:pietrick.hudhomme@univ-angers.fr)

Ilaria Ciofini - Chimie Paris Tech, PSL University, CNRS, Institute of Chemistry for Life and Health Sciences, 75005 Paris, France. [orcid.org/0000-0002-5391-4522](https://orcid.org/0000-0002-5391-4522)

Email: [ilaria.ciofini@chimieparistech.psl.eu](mailto:ilaria.ciofini@chimieparistech.psl.eu)

Authors

**Jules Schleinitz** - Laboratoire de Biomolécules (LBM), Département de Chimie, Sorbonne Université, École Normale Supérieure, PSL University, Sorbonne Université, CNRS, 75005 Paris, France. [orcid.org/0000-0001-7116-4772](https://orcid.org/0000-0001-7116-4772)

**Clara Chinchilla-Garzon** - Chimie Paris Tech, PSL University, CNRS, Institute of Chemistry for Life and Health Sciences, 75005 Paris, France.

**Anna Perfetto** - Chimie Paris Tech, PSL University, CNRS, Institute of Chemistry for Life and Health Sciences, 75005 Paris, France. [orcid.org/0000-0002-8145-7197](https://orcid.org/0000-0002-8145-7197)

Emile Escoudé - Laboratoire de Biomolécules (LBM), Département de Chimie, Sorbonne Université, École Normale Supérieure, PSL University, Sorbonne Université, CNRS, 75005 Paris, France.

Aline Makhloutah - Univ Angers, CNRS, MOLTECH-Anjou,
SFR Matrix, 49045 ANGERS,, France.
**Goeffrey Gontard** - Sorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, 75005, Paris, France.

**Maxime R. Vitale** - Laboratoire de Biomolécules (LBM), Département de Chimie, Sorbonne Université, École Normale Supérieure, PSL University, Sorbonne Université, CNRS, 75005 Paris, France. orcid.org/0000-0002-6740-2472

**Antoine Goujon** - Univ Angers, CNRS, MOLTECH-Anjou, SFR Matrix, 49045 ANGERS, France. orcid.org/0000-0002-8689-1021

**François-Xavier Felpin** - Nantes Université, CNRS, CEISAM UMR 6230, F-44000 Nantes, France. orcid.org/0000-0002-8851-246X

**Laurent Binet** - ChimieParisTech-PSL, PSL University, CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France. orcid.org/0000-0003-2591-3888

## Notes

The authors declare no competing financial interests.

## ACKNOWLEDGMENT

Authors are grateful to the University of Angers for PhD fellowship to A. M. and E. E. also gratefully acknowledges the ANR (ANR-20-CE07-0036; "PhotoFlat") for PhD fellowship. This work received financial support from the EUR LUMOMAT project with the Investments for the Future program ANR-18-EURE-0012. We thank ENS, PSL University, Sorbonne Université, University of Angers and the CNRS for financial support. We thank Mrs Julie Hemez (AMaCC, Nantes Université) for assistance with HRMS analyses. We thank Mrs Julie Hemez (AMaCC, Nantes Université) for assistance with HRMS analyses. We also thank Dr A. Bailly for preliminary results.

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