# Ortho O-Annulated AzaBenzannulated PeryleneDiimide and BisAzaCoroneneDiimide

Arthur David, Daryna Shymon, Hayley Melville, Lou-Ann Accou, Adèle Gapin, Magali Allain, Olivier Alévêque, Maximilien Force, Alexis Grosjean, Piétrick Hudhomme, et al.

► To cite this version:

Arthur David, Daryna Shymon, Hayley Melville, Lou-Ann Accou, Adèle Gapin, et al. Ortho O-Annulated AzaBenzannulated PeryleneDiimide and BisAzaCoroneneDiimide. Journal of Materials Chemistry C, 2023, 11 (42), pp.14631-14640. 10.1039/D3TC02376A. hal-04231811

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Distributed under a Creative Commons CC BY 4.0 - Attribution - International License
Ortho O-Annulated AzaBenzannulated PeryleneDiimide and
BisAzaCoroneneDiimide

Arthur H. G. David,ª Daryna Shymon,ª Hayley Melville,ª Lou-Ann Accou,ª Adèle Gapin,ª
Magali Allain,ª Olivier Alévêque,ª Maximilien Force,ᵇ Alexis Grosjean,ᵇ Piétrick Hudhomme,ª
Laura Le Bras*,** and Antoine Goujon*,**a

The development of new n-type organic semiconductors is crucial to the development of organic electronics. The introduction of heteroatoms into electron-acceptor units enables their properties to be fine-tuned and new applications to emerge. In this study, we present the preparation of BisAzaCoroneneDiimide derivatives annulated by the insertion of oxygen in their *ortho* position. These compounds exhibit high planarity and their properties are sensitive to the extension of their *π*-system. Their performance in preliminary organic electronics studies is also reported.

Introduction

Polycyclic aromatic hydrocarbons (PAHs) are fragments of graphene prepared in various sizes and shapes to adapt their optoelectronic properties.¹ This structure-property relationship allows material chemists to design conjugated materials with specific properties, tailored for organic electronics devices.² Introducing heteroatoms,³ such as nitrogen⁴ or sulfur,⁵ into their core is a powerful strategy to tune their frontier orbitals energy, as well as their optical, semiconducting and self-assembly properties. The inclusion of oxygen atoms⁶ in the skeleton of PAHs lead to applications ranging from chiroptics⁷ and spintronics⁸ to organic electronics⁹ and photocatalysis.¹⁰ Bonifazi and co-workers¹¹ have extensively studied the synthesis and properties of oxygen-doped PAHs resulting in a collection of functional conjugated systems for electrochromic displays,¹² photocatalysis,¹³ charge transport,¹⁴ and nonlinear optics.¹⁵ These oxygen-doped PAHs are prepared through a copper-catalysed oxidative C–H activation of hydroxy-decorated PAHs precursors.¹⁶ The vast majority of these materials are electron-rich, p-type materials. The exploration of electron poor, n-type, O-decorated PAHs lags behind and few examples have been reported so far. Notable examples are coming again from Bonifazi and co-workers¹⁷ who reported oxygen-containing rylene diimide and monoimide derivatives showing low LUMO energies and a wide visible-light absorption. Fujimoto and Izawa¹⁸ described a distorted *bay* O-annulated perylene diimide (PDI) derivative bearing seven-membered rings which has been exploited as a non-fullerene acceptor (NFA) in organic solar cells (OSCs). Recently, Zeng and co-workers¹⁹ reported the synthesis of an O-doped rylene diimide derivative showing efficient near-infrared fluorescence.

<footnote>ªUniv Angers, CNRS, MOLTECH-Anjou, SFR MATRIX, F-49000 Angers, France</footnote>

<footnote>ᵇUniversité de Franche-Comté, CNRS, Chrono-environnement, F-25000 Besançon, France</footnote>

<footnote>laura.le_bras@univ-fcomte.fr</footnote>

<footnote>antoine.goujon@univ-angers.fr</footnote>
To further explore the effect of the introduction of oxygen atoms in PAHs, we investigated the *ortho* O-annulation of Azabenzannulated PeryleneDiimides (AzaBPDIs) and BisAzaCoroneneDiimides (BACDs). Our group recently reported their efficient light-driven synthesis²⁰ and promising applications as semiconductors when heteroannulated,²¹ and NFAs in OSCs when multimerized.²² Herein, we prepared AzaBPDIs and BACDs presenting hydroxy groups in vicinity of their *ortho* position. Their *ortho* O-annulation offers planar electron-deficient materials, showing an increase of fluorescence and a deepening of their LUMO levels. Their ability to accept electrons and their strong absorption of visible light have been used to prepare organic field effect transistors (OFETs) and OSCs, revealing that O-annulated electron-deficient materials are worth investigating to design new high-performance materials for organic electronics.

<figure><img src="image_2.png" /><figcaption>**Fig. 1** Examples of O-incorporating rylene diimide dyes.</figcaption></figure>

## Results and Discussion

AzaBPDIs with aromatic side groups presenting a hydroxy group oriented toward the *ortho* position of the AzaBPDI should be efficiently cyclized into an oxygen-incorporating 6-member rings by copper-catalyzed oxidative C–H activation.¹⁶ AzaBPDI **1a, 1b, 3**, and BACD **5** and **7** were prepared *via* our recently reported²⁰ light-mediated azabenzannulation of PDIs methodology in good yields (see SI Scheme S1, S2, S3, S4 and S5). The annulation reaction afforded compounds **2a** and **2b** in a moderate 47% and a good 65% yields, respectively. The difference between the yields are attributed to the improved solubility of the 2-octyldodecyl peripheral chains compared to the pentyl ones. O-annulated AzaBPDI **4** featuring an extended $\pi$ system was obtained in 55% yield despite its poor solubility. BACD **5** was efficiently converted into a large double *ortho* O-annulated O-BACD **6**. The same reaction performed on BACD **7** afforded only traces of the target materials, along with unidentified decomposition products.
<figure><img src="image_3.png" /><figcaption>**Scheme 1.** Synthesis of O-annulated AzaBPDIs 2a,b, 4, BACDs 6 and 9 through copper-catalyzed oxidative C–H activation reactions.</figcaption></figure>

A non-symmetrical O-annulated BACD dimer with a central phenyl ring was prepared. The sequence involved a double visible-light azabenzannulation between regiorepure²³ 1,6-(NH₂)₂PDI **8** and isophthalaldehyde to obtain an amine-terminated dimer, subsequently reacted with an excess of salicylaldehyde in another azabenzannulation reaction. At last, the intermediate was engaged into a copper-catalysed oxidative C–H activation to afford dimer **9** in a very good 45% overall yield following seven synthetic steps. The combination of our light-mediated preparation of AzaBPDIs and BACDs combined to oxidative O-annulation reaction allowed us to efficiently fuse 3 additional aromatic rings to a PDI core in the case of compounds **2a** and **2b**, or 6 for BACD **6**. The non-symmetrical BACDs dimer **9** was obtained by the fusion of 8 new aromatic rings. All compounds exhibit good solubilities in common chlorinated or aromatic solvents, except for the naphthalene-extended dye **4** which was found to be only soluble in hot C₂H₂Cl₄. Single crystals of compound **2a** suitable for X-ray diffraction were grown (**Figure 1**) by slow evaporation of Et₂O in CH₂Cl₂ solutions of the compounds. The O-annulated AzaBPDIs are planar and the three added aromatic rings are parallel to the former PDI core (**Figure 1a**). The molecules crystallize as dimers separated by a distance of 3.3 Å (**Figure 1b**) demonstrating a tight π-stacking originating from strong donor-acceptor interactions, as the electron-rich side-groups of one molecule are interacting with the electron-deficient diimide core of the second one (**Figure 1c**). Furthermore, the
packing of **2a** displays columnar superstructures (**Figure 1d**) whose axes are alternatively deviated from
a 48° angle (**Figure 1e**).

<figure><img src="image_4.png" /><figcaption>**Figure 2.** (a) Top-down view of the X-ray diffraction structure of AzaBPDI 2a. (b) Side-on and (c) tilted view of the π-stack dimers of AzaBPDI 2a. Illustration of the packing of along the (d) b-axis and (e) c-axis. Hydrogen atoms were omitted for the sake of clarity. Color coding: C, grey; O, red; N, blue.</figcaption></figure>

The optoelectronic properties (Table 1) of the O-doped nanographenes were investigated by a combination of absorption/emission spectroscopy and cyclic voltammetry (CV). After annulation, the absorption profile of all compounds are shifted toward longer wavelengths (see Figures 3, S1, S9, S17 and S23). Compounds 2a and 2b show similar absorption spectra in solution (Figure 3a) displaying lowest energy maxima centered around 538 and 539 nm, respectively. The simple replacement of a phenyl ring by and a naphthalene unit in dye 4 leads to a significant red-shift of the lowest energy maximum to 562 nm (Figure 3b). These three molecules have absorption spectra featuring a vibronic progression of their lowest energy transition similar to that of regular PDIs. This is not the case for O-doped BACD 6 since an intense transition is observed at 387 nm associated with an ε exceeding 10⁶ M⁻¹ cm⁻¹ followed by a poorly defined absorption pattern ending in a sharper band at 526 nm (Figure 3c). Compared to mono-annulated derivatives 2a and 2b, BACD 6 displays a slightly blue-shifted and reduced absorption at low energy. The dimerized species 9 shows a similar absorption spectrum with a more well-defined pattern at low energy and a maximum at 524 nm. Solid-state absorption spectra were recorded by spin-coating 10 mg/mL CHCl₃ solutions of the dyes in on glass substrates, except for AzaBPDI 4 because of its poor solubility and processability preventing the formation of a homogeneous film. Compared to their absorption in solution, mono-annulated dyes 2a and 2b show a red shifted absorption and an inversion of ratio intensity between its two first absorption bands. This pattern is typical of the H-aggregate formation, which would be a possible explanation for this observation as face-to-face dimers can be seen in the crystal structure of 2a. In thin films, the double-annulated O-doped BACD derivative 6
see its lowest energy band shifting to larger wavelength while its absorption intensity increase compared to the following higher energy absorption band, an observation that could be explained by the formation of J-aggregates.²⁴

<table><caption>**Table 1.** Summary of the optoelectronic properties of AzaBPDIs **2a-b**, **4**, BACD **6**, and BACD dimer **9**.</caption><thead><tr><th>Compound</th><th>λ<sub>abs</sub> /<br>nm<sup>a</sup><br>sol.</th><th>ε /<br>M<sup>-1</sup>cm<sup>-1b</sup></th><th>λ<sub>abs</sub> /<br>nm<sup>a</sup><br>film</th><th>λ<sub>em</sub> /<br>nm</th><th>Φ<sub>f</sub> /<br>%</th><th>E<sup>LUMO</sup> /<br>eV</th><th>E<sup>HOMO</sup> /<br>eV</th><th>ΔE<sup>HOMO-LUMO</sup> /<br>eV</th></tr></thead><tbody><tr><td><b>2a</b></td><td>538</td><td>3.9 × 10<sup>4</sup></td><td>556</td><td>555</td><td>23</td><td>-3.66</td><td>-5.73</td><td>2.07</td></tr><tr><td><b>2b</b></td><td>539</td><td>3.8 × 10<sup>4</sup></td><td>557</td><td>556</td><td>29</td><td>-3.75</td><td>-5.84</td><td>2.09</td></tr><tr><td><b>4</b></td><td>562</td><td>1.6 × 10<sup>4</sup></td><td>N/A</td><td>586</td><td>4.3</td><td>-3.68</td><td>-5.80</td><td>2.12</td></tr><tr><td><b>6</b></td><td>526</td><td>2.0 × 10<sup>4</sup></td><td>530</td><td>532</td><td>5.4</td><td>-3.50</td><td>-5.76</td><td>2.26</td></tr><tr><td><b>9</b></td><td>524</td><td>2.7 × 10<sup>4</sup></td><td>525</td><td>537</td><td>4.3</td><td>-3.60</td><td>-5.86</td><td>2.26</td></tr></tbody></table>

<sup>a</sup>Maximum wavelength of the lowest energy absorption band. <sup>b</sup>Extinction coefficient of the lowest energy absorption band.

<figure><img src="image_5.png" /><figcaption>**Figure 3.** Absorption (solid line) and normalized emission (dashed lines) spectra of dyes **2a,b** (a, λ<sub>exc</sub>=500 nm), **4** (b, λ<sub>exc</sub>=500 nm), **6** (c, λ<sub>exc</sub>=475 nm), and **9** (d, λ<sub>exc</sub>=490 nm) recorded in CHCl<sub>3</sub> at a concentration of ca. 5×10<sup>-6</sup> M. Comparison between the normalized absorption spectra of AzaBPDI **2a** (e) and BACD **6** (f) in CHCl<sub>3</sub> solution (solid line) and as a thin film after annealing (dashed line).</figcaption></figure>
All compounds exhibit moderate to low fluorescence. For mono-annulated dyes **2a** and **2b**, the fluorescence quantum yields Φ<sub>f</sub> reach 23 and 29%, respectively, however it drops to 4.3% for the naphthalene decorated AzaBPI **4**. O-doped BACD **6** and dimer **9** are poorly fluorescent with Φ<sub>f</sub> of 5.4 and 4.3% respectively. All the O-annulated structures display small Stokes shifts, which is in agreement with their rigid structure. Cyclic Voltammetry (CV) was performed to determine the energy of the frontier orbitals of the O-annulated diimide molecules. All compounds show two reduction waves typical of PDI dyes when scanning toward negative potential. Mono-annulated compounds **2a**, **2b** and **4** are good electron acceptors with LUMO energies estimated at -3.66 eV, -3.75 eV and -3.68 eV, respectively. *Ortho* extended BACD **6** has a slightly uplift LUMO level sitting at -3.50 eV, at the limit of what could be considered a good electron-accepting material. Dimer **9** remains slightly more electron-deficient with a LUMO energy of -3.60 eV. Overall the O-annulation reduces the optical band gap of the AzaBPDIs or BACDs precursors, by uplifting the HOMO energy while have a similar but less pronounced effect on LUMO energies.

By using (TD-)DFT formalism the electronic ground state properties of compounds **2**, **4**, **6**, and **9** have been computed. Within an implicit solvation model (chloroform), at the B3LYP/6-31+G(d) level of theory,²⁵ the vertical absorption bands were retrieved and a systematic comparison with experimental data was conducted. The details of the computational approach are gathered in the Supporting Information. All the molecules were optimized, and a frequency calculation has been performed in each case to ensure that the molecules were in a minimum of the potential energy surface. As expected, compounds **2a**, **2b**, **4**, and **6** are planar molecules. For **9**, there are possible rotations around the central phenyl moiety, and to account this flexibility, molecular dynamics (MD) simulations (see the Supporting Information for more details) were considered. It resulted in a non-planar structure for **9**, with a tilt between the central phenyl moiety and the side part from 40° to up to 120° (**Figure 5** and **S44**). The movement of each side of the molecule is independent from the other one. This flexibility has been considered for the calculation of the optical properties. As already observed in our previous study,²³ the lateral chains were not considered as they do not have an influence on the optical properties and thus compounds **2a** and **2b** were equivalent for the computational part and denoted as **2**. For all compounds, the lateral chains were replaced with a methyl group. The experimental and computed spectra (**Figure S45** and **Table 2**) show a good agreement and the differences in terms of blue- or red-shift are also retrieved. For **2** (**4**), the first absorption band, experimentally at 539 nm (562 nm), corresponds to a HOMO-LUMO transition and is ascribed to a S₀ → S₁ excitation (**Table 2**) at 536 nm (582 nm). Experimentally, for **6** and **9**, the area around 400 nm shows an increase of its molar extinction coefficient when compared to **2** and **4**, leading to a main absorption band. The experimental transitions at 387 nm and 366 nm for **6** and **9**, respectively, are computed at 380 nm and 367 nm respectively (**Table 2**). One can notice that the oscillator strength of **6** and **9** in the 400 nm area are larger than the ones of **2** and **4** in the same area (0.75 and 0.86 for **6** and **9** vs 0.58 and 0.67 for **2** and **4**), indicating the same trend as the one observed experimentally.

**Table 2.** Experimental (λ<sub>abs</sub>, nm) and calculated (λ<sub>calc</sub>, nm) absorption for molecules **2**, **4**, **6** and **9**. The absolute energy difference between experimental and calculated λ (|ΔΕ|, in eV), the attribution and the description of the transition, the corresponding oscillator strength (f), the charge-transfer distance (d<sub>CT</sub>, in Å), amount of transferred electron (q<sub>CT</sub>, in |e|), and the norm of transition dipole moment, (||μ̄<sub>CT</sub>||, in D), have also been reported for each transition.
<table><thead><tr><th>Compound</th><th>λ<sub>abs</sub></th><th>λ<sub>calc</sub></th><th>|ΔE|</th><th>Attribution</th><th>Description</th><th>f</th><th>d<sub>CT</sub></th><th>q<sub>CT</sub></th><th>||μ&#773;<sub>CT</sub>||</th></tr></thead><tbody><tr><td rowspan="2">2</td><td>539</td><td>536</td><td>0.01</td><td>S<sub>0</sub> → S<sub>1</sub></td><td>H → L</td><td>0.41</td><td>3.35</td><td>0.51</td><td>8.13</td></tr><tr><td>376</td><td>376</td><td>0.00</td><td>S<sub>0</sub> → S<sub>4</sub></td><td>H → L+1</td><td>0.58</td><td></td><td></td><td></td></tr><tr><td rowspan="2">4</td><td>562</td><td>582</td><td>0.08</td><td>S<sub>0</sub> → S<sub>1</sub></td><td>H → L</td><td>0.30</td><td>3.64</td><td>0.55</td><td>9.59</td></tr><tr><td>398</td><td>403</td><td>0.04</td><td>S<sub>0</sub> → S<sub>4</sub></td><td>H → L+1</td><td>0.67</td><td></td><td></td><td></td></tr><tr><td rowspan="3">6</td><td>526</td><td>518</td><td>0.04</td><td>S<sub>0</sub> → S<sub>1</sub></td><td>H → L</td><td>0.21</td><td>1.27</td><td>0.48</td><td>2.94</td></tr><tr><td>474</td><td>482</td><td>0.04</td><td>S<sub>0</sub> → S<sub>2</sub></td><td>H-1 → L</td><td>0.21</td><td></td><td></td><td></td></tr><tr><td>387</td><td>380</td><td>0.06</td><td>S<sub>0</sub> → S<sub>4</sub></td><td>H-1 → L+1</td><td>0.75</td><td>1.48</td><td>0.47</td><td>3.33</td></tr><tr><td rowspan="3">9_3</td><td>524</td><td>535</td><td>0.05</td><td>S<sub>0</sub> → S<sub>1</sub></td><td>H → L</td><td>0.22</td><td></td><td></td><td></td></tr><tr><td>524</td><td>531</td><td>0.03</td><td>S<sub>0</sub> → S<sub>2</sub></td><td>H, H-1 → L+1</td><td>0.17</td><td></td><td></td><td></td></tr><tr><td>366</td><td>367</td><td>0.01</td><td>S<sub>0</sub> → S<sub>19</sub></td><td>H-2 → L+3</td><td>0.86</td><td>4.15</td><td>0.89</td><td>17.66</td></tr></tbody></table>

All the orbitals involved in the previously mentioned transitions have been analyzed (Figures 4, S46 and S47). The same behavior is observed for 2 and 4, with a π-π* transition, originally located on the whole molecule and going up to the perylene core of the molecule. Due to the asymmetry of both compounds, the charge-transfer (CT) character is non-negligible, and all the descriptors are quite large (Table 2, Figure S48). For 6, the main absorption band corresponds to a HOMO-1-LUMO+1 transition and in this case the whole molecule is involved. Because of the symmetry the CT character is low with the lowest values of the four compounds for the all the descriptors.

<figure><img src="image_6.png" /><figcaption>**Figure 4.** Representation of molecular orbitals involved in the first (2, 4) or most intense (6, 9) transition. Isodensity=0.0004 a.u.</figcaption></figure>

For 9, due to the flexibility, different structures were considered to compute the optical properties. After the analysis of the evolution of the relative position of the perylene core around the central phenyl (Figure 5b,c), some preferential conformations were extracted from MD simulation with three representative dihedral couples, [120, -40] for 9_1, [90, -70] for 9_2, and [50, -60] for 9_3. If the corresponding optical
properties are globally similar among the different structures (Tables 2 and S2) some small differences can nevertheless be observed. Depending on the dihedral couple, the molecule is more or less conjugated, and it results in a slight blue- or red-shift of the absorption peaks. The orbitals that are involved in the transitions (Figure 4 and S47) can involve only one side of the molecule or both sides, inducing a large CT character. Thus, depending on the structure, the CT character can vary but is always the largest among the four molecules of this study. Consequently, the optoelectronic properties of 9 result from the different possible conformations of the compound which render the investigation of the flexibility of BACD dimers of major importance for targeted properties.

<figure><img src="image_7.png" /><figcaption>**Figure 5.** Definition of the two dihedral angles, α and β, representative of the position of both sides of the molecule with respect to the central phenyl group (a). Evolution of α (b) and β (c) along the 20 ns of MD simulation. To ease the comprehension, the most probable dihedral angles are highlighted with a straight line. Experimental (solid line) and computed (peaks) absorption spectra for three probable dihedral angle couples [α, β], [120, -40] (d), [90, -70] (e), [50, -60] (f).</figcaption></figure>

As preliminary exploration of the potential of such O-annulated diimide structures in organic electronics, dimer 9 was investigated as a NFA for organic solar cells. After an optimization process detailed in Table S3, the highest power conversion efficiency (PCE) was recorded for cells where dye 9 was combined with the donor polymer **PTB7-Th** (PCE10) in 1:1 ratio, in an inverse architecture prepared as follows: Glass:ITO:ZnO:**PTB7-Th**/9:MoO3:Ag (**Figure 6a**). The active layer was spin-coated from a chlorobenzene solution with 3% 1-chloronaphthalene as additive and subsequently thermally annealed. The absorption spectrum of the thin film (**Figure 6b**) reveals that if a good complementarity is observed, the contribution of compound 9 is significantly lower than the donor polymer **PTB7-Th**. A PCE of 1.58% was recorded for the best performing solar cell (**Figure 6c**), a modest value which can be nevertheless considered encouraging considering that such rylene diimide have never been studied as NFA before. To estimate the contributions of the donor and acceptor to the generation of photocurrent, an extern quantum efficiency (EQE) spectrum was recorded (**Figure 6d**), revealing a spectrum similar to **Figure 6b**.
Remarkably, the contribution of the NFA **9** to the generation of the photocurrent is higher than its
contribution to the overall absorbance of light in thin film observed in **Figure 6b**, revealing a more
balanced contribution of both components than expected.

<figure><img src="image_8.png" /><figcaption>**Figure 6.** Organic solar cells with compound **9** as NFA. a) Architecture of the optimized cell. b) Absorption spectra of a spin-coated films obtained from a 10 mg mL⁻¹ CHCl₃ solution of PTB7-Th:9 (1:1). c) I/V curves in the dark and under illumination of the best solar cell. d) EQE spectra of the cell.</figcaption></figure>

Soluble mono-annulated materials **2a**, **2b** and **6** were used as active layers in solution-processed bottom-gate top-contact (BGTC) Organic Field-Effect Transistors (OFETs). Their preparation and testing are detailed in the Supplementary Information (**Table S6** and **Figure S51-52**). Only compound **6** displayed a field-effect behavior but with good average V<sub>Th</sub> of 14 V, poor I<sub>on</sub>/I<sub>off</sub> and an average electron mobility of μ<sub>e</sub> = 3.06 × 10<sup>-5</sup> cm<sup>2</sup> V<sup>-1</sup> s<sup>-1</sup>. Again, these results are promising considering the fact that such O-doped BACDs have never been investigated before as active layers in solution-processed BGTC OFETs. Improvement of their performance will be investigated in the future and could be driven from device optimization<sup>2b,26</sup> and/or the molecular design, especially on the side chains which have a direct impact on the orientation of the organic semiconductors, thus, on the OFETs performances.<sup>27</sup>

**Conclusion**

The introduction of heteroatoms into electron-deficient scaffolds is a compelling strategy to tune their
properties. Herein we show how the *ortho* O-annulation of AzaBPDIs and BACDs shrinks their optical
gaps by uplifting their HOMO energies along with their LUMO energies in a less pronounced way. Such
derivatives seem to be highly sensitive to the nature of the new ring fused to their core as the naphthalene
appended derivative **4** shows a significant red-shift of its absorption compared to the phenyl-annulated **2a** and **2b**. Their preliminary use in organic electronic devices such as OSCs and OFETs demonstrates that more complex O-annulated rylene diimide structures are worth investigating to extend this so far small family of n-type organic semiconductors.

## Conflicts of interest

There are no conflicts to declare

## Acknowledgements

The authors acknowledge the Université d'Angers and SFR MATRIX for the access to the CARMA platform, Dr. Ingrid Freuze for Mass Spectrometry measurements, Benjamin Siegler for NMR experiments. L. L. B thanks the supercomputer facilities of the Mésocentre de calcul de Franche-Comté. Dr. Chloé Dindault and Dr. Maurizio Mastropasqua Talamo are acknowledged for their guidance in the preparation of OFETs. This work received financial support under the EUR LUMOMAT project and the Investments for the Future program ANR-18-EURE-0012 for D. S. and L-A. A. as Master LUMOMAT students. This work received support from the "Etoiles Montantes" funding scheme (A. G., project CURVY, 2021_11614) funded by the PULSAR 2021 program from the Région Pays de la Loire and the Université d'Angers, and the Agence Nationale de la Recherche (A. G., PhotoSynth ANR JCJC 2021, ANR-21-CE06-0015-01). Consequently, a CC-BY public copyright license has been applied by the authors to the present document and will be applied to all subsequent versions up to the Author Accepted Manuscript arising from this submission, in accordance with the grant's open access conditions (Creative Commons CC-BY 4.0 Licence: https://creativecommons.org/licenses/by/4.0/).

<figure><img src="image_9.png" /></figure>

## Author Contributions

A. H. G. David performed the synthesis and optoelectronic characterization of the materials, with contributions from D. Shymon, L.-A. Accou and A. Gapin. X-ray analysis was performed by M. Allain. Calculations were conducted and interpreted by L. Le Bras with contributions from M. Force and A. Grosjean. H. Melville performed the fabrication and measurements of organic electronic devices with contribution from O. Alévêque. A. H. G. David, L. Le Bras and A. Goujon wrote the manuscript with comments from all co-authors. A. Goujon conceived the work, with contributions from P. Hudhomme, directed it and was involved in every task except the calculations.

## Notes and references

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3 For recent reviews on PAHs incorporating heteroatoms, see: (a) X.-Y. Wang, X. Yao, A. Narita and K. Müllen, *Acc. Chem. Res.*, 2019, **52**, 2491; (b) A. Borissov, Y. K. Maurya, L. Moshniaha, W.-S. Wong, M. Żyla-Karwowska and M. Stępień, *Chem. Rev.*, 2022, **122**, 565; (c) T. Delouche, M. Hissler and P.-A. Bouit, *Coord. Chem. Rev.*, 2022, **464**, 214553.

4 For selected examples of nitrogen-containing PAHs, see: (a) H. Valdés, M. Poyatos and E. Peris, *Organometallics*, 2015, **34**, 1725; (b) R. K. Gupta, S. K. Pathak, B. Pradhan, D. S. S. Rao, S. K. Prasad and A. S. Achalkumar, *Soft Matter*, 2015, **11**, 3629; (c) Y. S. Park, D. J. Dibble, J. Kim, R. C. Lopez, E. Vargas and A. A. Gorodetsky, *Angew. Chem. Int. Ed.*, 2016, **55**, 3352; (d) A. D. Hendsbee, J.-P. Sun, W. K. Law, H. Yan, I. G. Hill, D. M. Spasyuk and G. C. Welch, *Chem. Mater.*, 2016, **28**, 7098; (e) C. J. Evoniuk, G. dos Passos Gomes, S. P. Hill, S. Fujita, K. Hanson and I. V. Alabugin, *J. Am. Chem. Soc.*, 2017, **139**, 16210; (f) X.-Y. Wang, M. Richter, Y. He, J. Björk, A. Riss, R. Rajesh, M. Garnica, F. Hennersdorf, J. J. Weigand, A. Narita, R. Berger, X. Feng, W. Auwärter, J. V. Barth, C.-A. Palma and K. Müllen, *Nat. Commun.*, 2017, **8**, 1948; (g) D. Cortizo-Lacalle, J. P. Mora-Fuentes, K. Strutyński, A. Saeki, M. Melle-Franco and A. Mateo-Alonso, *Angew. Chem. Int. Ed.*, 2018, **57**, 703; (h) A. Skabeev, U. Zschieschang, Y. Zagranyarski, H. Klauk, K. Müllen and C. Li, *Org. Lett.*, 2018, **20**, 1409; (i) H. Yokoi, S. Hiroto, D. Sakamaki, S. Seki and H. Shinokubo, *Chem. Sci.*, 2018, **9**, 819; (j) K. Oki, M. Takase, S. Mori and H. Uno, *J. Am. Chem. Soc.*, 2019, **141**, 16255; (k) A. Hirono, H. Sakai, S. Kochi, T. Sato and T. Hasobe, *J. Phys. Chem. B*, 2020, **124**, 9921; (l) T. Okamoto, S. Kumagai, E. Fukuzaki, H. Ishii, G. Watanabe, N. Niitsu, T. Annaka, M. Yamagishi, Y. Tani, H. Sugiura, T. Watanabe, S. Watanabe, J. Takeya, *Sci. Adv.*, 2020, **6**, eaaz0632; (m) J. Nebauer, C. Neiß, M. Krug, A. Vogel, D. Fehn, S. Ozaki, F. Rominger, K. Meyer, K. Kamada, D. M. Guldi, A. Görling and M. Kivala, *Angew. Chem. Int. Ed.*, 2022, **61**, e202205287; (n) X. Tian, K. Shoyama and F. Würthner, *Chem. Sci.*, 2023, **14**, 284.

5 For selected examples of sulfur-containing PAHs, see: (a) L. Meng, T. Fujikawa, M. Kuwayama, Y. Segawa and K. Itami, *J. Am. Chem. Soc.*, 2016, **138**, 10351; (b) P. E. Hartnett, H. S. S. R. Matte, N. D. Eastham, N. E. Jackson, Y. Wu, L. X. Chen, M. A. Ratner, R. P. H. Chang, M. C. Hersam, M. R. Wasielewski and T. J. Marks, *Chem. Sci.*, 2016, **7**, 3543; (c) X. Yang, F. Rominger and M. Mastalerz, *Org. Lett.*, 2018, **20**, 7270; (d) L. Li, S. Zhao, B. Li, L. Xu, C. Li, J. Shi and H. Wang, *Org. Lett.*, 2018, **20**, 2181; (e) Q. Deng, E. Zhou, Y. Huang, W. Qing, H. Zhai, Z. Liu and Z. Wei, *Chem. Commun.*, 2019, **55**, 4379; (f) S. Moon, Y. Nishii and M. Miura, *Org. Lett.*, 2019, **21**, 233; (g) B. Li, W. Peng, S. Luo, C. Jiang, J. Guo, S. Xie, Y. Hu, Y. Zhang and Z. Zeng, *Org. Lett.*, 2019, **21**, 1417; (h) L. Chen, P. Xia, T. Du, Y. Deng and Y. Xiao, *Org. Lett.*, 2019, **21**, 5529; (i) X. Li, H. Wang, H. Nakayama, Z. Wei, J. A. Schneider, K. Clark, W.-Y. Lai, W. Huang, J. G. Labram, J. R. de Alaniz, M. L. Chabinyc, F. Wudl and Y. Zheng, *ACS Appl. Energy Mater.*, 2019, **2**, 3805; (j) S. Tang, L. Zhang, H. Ruan, Y. Zhao and X. Wang, *J. Am. Chem. Soc.*, 2020, **142**, 7340; (k) J. Urieta-Mora, M. Krug, W. Alex, J. Perles, I. Fernández, A. Molina-Ontoria, D. M. Guldi and N. Martín, *J. Am. Chem. Soc.*, 2020, **142**, 4162; (l) K. P. Kawahara,
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6 For selected examples of oxygen-containing PAHs, see: (a) N. Lv, M. Xie, W. Gu, H. Ruan, S. Qiu, C. Zhou and Z. Cui, *Org. Lett.*, 2013, **15**, 2382; (b) Y. Okamoto, M. Tanioka, A. Muranaka, K. Miyamoto, T. Aoyama, X. Ouyang, S. Kamino, D. Sawada and M. Uchiyama, *J. Am. Chem. Soc.*, 2018, **140**, 17857; (c) B. Liu, D. Shi, Y. Yang, D. Liu, M. Li, E. Liu, X. Wang, Q. Zhang, M. Yang, J. Li, X. Shi, W. Wang and J. Wei, *Eur. J. Org. Chem.*, 2018, 869; (d) S. M. Elbert, M. Reinschmidt, K. Baumgärtner, F. Rominger and M. Mastalerz, *Eur. J. Org. Chem.*, 2018, 532; (e) C. M. Wehrmann, R. T. Charlton and M. S. Chen, *J. Am. Chem. Soc.*, 2019, **141**, 3240; (f) M. K. Węcławski, I. Deperasińska, M. Banasiewicz, D. C. Young, A. Leniak and D. T. Gryko, *Chem. Asian J.*, 2019, **14**, 1763; (g) W. Xue, D. Wang, C. Li, Z. Zhai, T. Wang, Y. Liang and Z. Zhang, *J. Org. Chem.*, 2020, **85**, 3689; (h) A. Vladimir, F. Mikhail and K. Amsharov, *RSC Adv.*, 2020, **10**, 10879; (i) X. Chen, L. Yan, Y. Liu, Y. Yang and J. You, *Chem. Commun.*, 2020, **56**, 15080; (j) V. Bhat S., M. Vadivel, D. P. Singh, V. A. Raghunathan, A. Roy and S. Kumar, *Chem. Eur. J.*, 2023, **29**, e202300227; (k) T. Luo, Y. Wang, J. Hao, P.-A. Chen, Y. Hu, B. Chen, J. Zhang, K. Yang and Z. Zeng, *Angew. Chem. Int. Ed.*, 2023, **62**, e202214653; (l) T. Shoji, N. Sakata, Y. Ariga, A. Yamazaki, R. Katoh, T. Okujima, R. Sekiguchi and S. Ito, *Chem. Commun.*, 2023, **59**, 3447.

7 (a) K. Takaishi, S. Hinoide, T. Matsumoto and T. Ema, *J. Am. Chem. Soc.*, 2019, **141**, 11852; (b) H. Chang, H. Liu, E. Dmitrieva, Q. Chen, J. Ma, P. He, P. Liu, A. A. Popov, X.-Y. Cao, X.-Y. Wang, Y. Zou, A. Narita, K. Müllen, H. Peng and Y. Hu, *Chem. Commun.*, 2020, **56**, 15181; (c) J. Wade, J. R. Brandt, D. Reger, F. Zinna, K. Y. Amsharov, N. Jux, D. L. Andrews and M. J. Fuchter, *Angew. Chem. Int. Ed.*, 2021, **60**, 222.

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9 (a) N. Kobayashi, M. Sasaki and K. Nomoto, *Chem. Mater.*, 2009, **21**, 552; (b) N. C. Davy, G. Man, R. A. Kerner, M. A. Fusella, G. E. Purdum, M. Sezen, B. P. Rand, A. Kahn and Y.-L. Loo, *Chem. Mater.*, 2016, **28**, 673; (c) N. Xu, Y. Li, R. Wu, R. Zhu, J. Zhang, S. M. Zakeeruddin, H. Li, Z.-S. Li, M. Grätzel and P. Wang, *Chem. Eur. J.*, 2019, **25**, 945; (d) G. Giesbers, J. Van Schenck, A. Quinn, R. Van Court, S. M. Vega Gutierrez, S. C. Robinson and O. Ostroverkhova, *ACS Omega*, 2019, **4**, 13309.

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**Graphical Abstract**
<figure><img src="image_10.png" /></figure>

Ortho O-annulated
BisAzaCoroneneDiimides

Electron-Accepting Material
Non-Fullerene Acceptor

<figure><img src="image_11.png" /></figure>