# Design and synthesis of new Pentacene derivatives containing Dimethoxydiphenylamine arms and theoretical study

Zeinab Kadi, Sebastien Peralta, Clément Cabanetos, Marwan Kobeissi, Bruno

Schmaltz

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Zeinab Kadi, Sebastien Peralta, Clément Cabanetos, Marwan Kobeissi, Bruno Schmaltz. Design and synthesis of new Pentacene derivatives containing Dimethoxydiphenylamine arms and theoretical study. Journal of Molecular Structure, 2025, 1334, pp.141701. 10.1016/j.molstruc.2025.141701. hal-05345249

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# Design and synthesis of new Pentacene derivatives containing Dimethoxydiphenylamine arms and theoretical study

Zeinab Kadi<sup>a,*</sup>,<sup> ID </sup> Sebastien Peralta<sup>b</sup>, Clément Cabanetos<sup>d,e</sup>, Marwan Kobeissi<sup>c,*</sup>,
Bruno Schmaltz<sup>a</sup>

## ARTICLE INFO

**Keywords:**

Organic semiconductors
Pentacene
Dimethoxyphenylamin (DMPA)
Carbazole-DMPA arms
DFT calculations

## ABSTRACT

In a quest of exploitation of soluble and stable pentacene derivatives for organic electronics devices or for interface layers in perovskite solar cells, a novel series of arylamine-capped pentacene derivatives namely DMPA (Ph)Pent, DMPA(Ph)₂Pent, DMPA(Ph)₃Pent, and Cz(Ph)Pent were synthesized, characterized, and studied. Two key parameters were investigated in this work: i) the length of the aryl spacer and ii) the substitution of dimethoxyphenylamine (DMPA) arms with carbazole-DMPA arms, to study their effects on the structure-property relationship. These unprecedented compounds, synthesized via a two-step, showed excellent solubility and stability as a result of the introduction of DMPA and carbazole-DMPA arms. The HOMO-LUMO energy gaps were calculated through experimentally and theoretically. These new pentacene derivatives exhibited high thermal stability, with decomposition temperatures around 470 °C and high rigidity with glass transition temperatures ranging from 125 °C to 231 °C. These promising thermal and electrochemical properties highlight these new soluble and stable materials as potential strong candidates for a range of applications, including organic thin-film transistors and interface layers in perovskite solar cells.

## 1. Introduction

Organic semiconductors based on extended aromatic systems at-
tracts a great attention as a basic material used in the field of “organic
electronics” in the form of light-emitting diodes, field-effect transistors
and photovoltaic cells [1–7]. Among the oligocenes containing two to
five benzene rings, pentacene is one of the most basic semiconductor
materials studied and used in organic thin-film transistors that has been
considered to be a benchmark p-type organic semiconductor. Planarity,
aromaticity, redox properties and ability to form crystalline films [8,9]
have allowed the utilization of pentacene extensively in the field of
organic electronics, which have demonstrated high hole field effect
mobility of μ<sub>FET</sub> = 1.1 cm<sup>2</sup>/V.s on hard alumina, 3.3 cm<sup>2</sup>/V. s on a soft
polymer substrate and 35 cm<sup>2</sup> V/s for a single crystal at room temper-
ature [10–12]. The carrier mobility of pentacene depends upon various
factors, such as the molecular orientation, the grain size within the de-
vice and the presence of impurities [13]. The pentacene materials

π-stacked arrays in the solid state lead to devices with significantly
higher charge mobility's. However, the main drawbacks are poor solu-
bility in organic solvents, delicate purification, fabrication which re-
quires high vacuum evaporation and stability in solution do to
degradation in oxygen and light environment [14–17]. Indeed, the
C-6/C-13 positions of pentacene are extremely sensitive to oxygen in
solution. The double bonds of the central ring shows a radical character,
due to which it results in an increment of reactivity to oxygen and for-
mation of the transannular endoperoxide. [18,19] Different approach
has been demonstrated to overcome the photooxidation and to enhance
the solubility by the substitution of the C-6 and C-13 positions of pen-
tacene. [15,20] In 2001, Anthony and co-workers reported the synthesis
of a stable and soluble 3,6-disubstituted pentacene derivative containing
triisopropylsilylethynyl (TIPS) groups, introduced via an alkyne spacer
to the pentacene core. [21] They demonstrated that the direct attach-
ment of silyl groups to the pentacene core would disrupt the π-stacking
interactions. The presence of alkyne spacer, is necessary to maintain the

<footnote><sup>a</sup> Laboratoire de Physico-Chimie des Matériaux et des Electrolytes pour l'Energie (PCM2E), EA6299, Université de Tours, Parc Grandmont, 37200 Tours, France</footnote>

<footnote><sup>b</sup> CY Cergy Paris Université, LPPI, F-95000 Cergy, France</footnote>

<footnote><sup>c</sup> Laboratoire Rammal Rammal, Equipe de Synthèse Organique Appliquée SOA, Université Libanaise, Faculté des Sciences 5, Nabatieh 6573/14, Lebanon</footnote>

<footnote><sup>d</sup> Univ Angers, CNRS, MOLTECH-ANJOU, SFR MATRIX, F-49000 Angers, France</footnote>

<footnote><sup>e</sup> Building Blocks for Future Electronics Laboratory (2BFUEL), IRL2002, CNRS -Yonsei University, Seoul, South Korea</footnote>

<footnote>* Corresponding authors.
E-mail addresses: zeinab.kadi@cyu.fr (Z. Kadi), mkobeissi@ul.edu.lb (M. Kobeissi).</footnote>
structural integrity for efficient π-π interactions [22]. In order to enhance the photostability and solubility of pentacene, Ong et al. introduced a novel approach by incorporating various functional groups, including aryl groups, alkyl chains and fluorine atoms to the pentacene core, connected via a triple bond as a spacer. [23] They establish that the stability of the pentacene could be significantly improved at the C-6 and C-13 positions through extended π-electron delocalization, which arises from resonance and inductive effects associated with the substituents. In parallel, the integration of two phenyl groups connected by a triple bond at the C-6 and C-13 positions of pentacene enhance the stability compared to 3,6-alkyl-disubstituted pentacenes. [23] Furthermore, 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) has been reported and has demonstrated charge carrier mobilities exceeding 1.0 cm²/V·s in organic field-effect transistors. Regarding the chemical structure, the bulky group substitution promote a face-to-face molecular orientation, leading to increased π-orbital overlap [24–26]. Despite these promising attributes, the use of pentacene as a hole-transporting material (HTM) in perovskite solar cells (PSCs) remains constrained due to its limited solubility in organic solvents and reduced chemical stability. In 2015, Kazim et al. reported the use of the same semiconductor TIPS-pentacene as a hole transporting material (HTM) in perovskite solar cells. The TIPS-pentacene exhibits notable thermal stability up to 380 °C, with a glass transition temperature $T_g$ of 122 °C, and a power conversion efficiency of 11.8 %. [27] Indeed, up to new the use of pentacene as a hole transporting material, interface layers in perovskite solar cells or for organic electronics is still limited due to the low solubility and low stability in organic solvents [27]. A key focus in this field is the functionalization of pentacene, to enhance its stability and solubility. The selection of substituents on the pentacene core must be chosen with great care, as these parameters play a key role to obtain a stable and soluble material's in organic solvents.

In this study, we present the synthesis of a novel soluble and stable pentacene derivatives, which structure is represented in Fig. 1. These unprecedented compounds were prepared through a two-step reaction starting with a double nucleophilic addition on the carbonyl groups of 6,13-pentacenequinone followed by a palladium-catalysed cross coupling reaction (Scheme 1). With interesting electrochemical

properties, good solubility, high thermal stabilities and rigidity, two dimethoxydiphenylamine (DMPA) arms were introduced onto a penta-cene core through a 1–3 phenyls spacer. Additionally, the DMPA units were replaced by carbazole-DMPA arms and similarly incorporated into the pentacene core using one phenyl as spacer. Herein, a special emphasize was put on both the length of the spacers (1, 2 and 3 phenyl units) and the replacement of DMPA by the carbazole-DMPA arm to rationalize their effects on the physico-chemical properties in order to establish a certain structure-properties. Our research has been focused towards arylamine derivatives, as previously reported in studies [28–36] which are being utilized for the first time in the synthesis of pentacene derivatives in this work. The arylamine derivatives exhibit promising electrochemical properties and high thermal stability making them of particular interest for our research. These characteristics distinguish them from other functional groups, such as alkyl or silyl groups, that have been introduced into the pentacene core. As well, the presence of methoxy (OMe) groups, along with an increase in their number through the substitution of DMPA with carbazole-DMPA, offer a promising strategy for enhancing interactions with the perovskite layer in case of use of these materials as interface layers in perovskite solar cells [35]. The presence of additional methoxy groups could potentially improve the interfacial contact between the HTM and the perovskite, by improving overall device performance [35]. The rigidity of these new materials can help to enhance the protection of the perovskite layer against humidity. The optical, electronic, thermal properties and solubility were studied depending on the nature of the arms and the length of spacer between the arm and the pentacene core.

## 2. Results and discussion

### 2.1. Synthesis of DMPA(Ph)Pent, DMPA(Ph)₂Pent, DMPA(Ph)₃Pent and Cz(Ph)Pent

The synthetic route used to prepare DMPA(Ph)Pent, DMPA(Ph)₂Pent, DMPA(Ph)₃Pent and Cz(Ph)Pent is illustrated in Scheme 1. The synthesis of the precursor N3, N3, N6, N6-tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine (2), 4-methoxy-N-(4-methoxyphenyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)

<figure><img src="image_4.png" /><figcaption>Fig. 1. Chemical structure of the prepared pentacene based derivatives.</figcaption></figure>
<figure><img src="image_5.png" /><figcaption>**Scheme 1.** Synthetic Procedures for DMPA(Ph)Pent, DMPA(Ph)₂Pent, DMPA(Ph)₃Pent and Cz(Ph)Pent. <sup>a</sup>Reagents and conditions: (a) 1) n-BuLi, -78 °C 2) pentacene-quinone, -78 °C 3) SnCl₂·2H₂O, 1 h, reflux, THF, (b) NaOtBu, Pd₂dba₃, P(t-Bu)₃, 24 h, reflux, Toluene; (c) NaOtBu, Pd(OAc)₂, P(t-Bu)₃, 24 h, reflux, Toluene; (d) Pd(PPh₃)₄, K₂CO₃, 100 °C, 16 h, Toluene / THF/H₂O; (e) Pd(PPh₃)₄, K₂CO₃, 110 °C, 16 h, Toluene / THF/H₂O</figcaption></figure>

phenyle) aniline (3) followed earlier attempts [37]. First, 4,4-dibromo-benzene was treated with 6 eq. of n-Butyllithium in THF at -78 °C to generate the corresponding lithium salt, which was readily reacted with pentacene-quinone followed by an in-situ reduction using SnCl₂·2H₂O to afford 6, 13-bis (4-bromophenyl) pentacene (PhBr₂)₂Pent in 69 % yield. Buchwald-Hartwig cross-coupling between (PhBr₂)₂Pent and 4, 4'-dimethoxydiphenylamine is then carried out using the tris(dibenzy-lideneacetone)dipalladium [Pd₂(dba)₃] as catalyst in toluene at 110 °C to give compound DMPA(Ph)Pent in 48 % yield. Using the N3, N3, N6, N6-tetrakis (4-methoxyphenyl)-9H-carbazole-3,6-diamine in the presence of Palladium(II) acetate Pd(OAc)₂ in toluene at 120 °C gave Cz(Ph)Pent in 35 % yield. Under the same conditions but with varying the amine, the Buchwald coupling worked with the carbazole and not with the DMA in the presence of palladium acetate. This could be probably explained by the fact that the carbazole being richer in electrons than DMA, facilitates thus the reduction of Pd(OAc)₂ from Pd(II) to the active species Pd(0) prior to the catalytic cycle. Furthermore, the higher degree of conjugation in the carbazole-DMPA increases its reactivity and accelerates the oxidative addition to palladium catalyst. A Suzuki coupling between compound (PhBr₂)₂Pent and the corresponding boronic derivative in presence of tetrakis(triphenylphosphine)palladium [Pd(PPh₃)₄] in a mixture of toluene/THF/H₂O (4/4/2) resulted in the formation of DMPA(Ph)₂Pent and DMPA(Ph)₃Pent in 45 % and 22 % yield respectively. It is to be noted that a nucleophilic addition performed between 4,4-dibromobiphenyl and 6,13-pentacene-diquinone according to the same conditions used for 4,4-dibromophenyl yielded a product that degraded upon purification. Consequently, only a spacer with one phenyl ring is introduced, following this methodology. The structure and purity of all intermediates and final products were confirmed by NMR spectroscopy (¹H and ¹³C) as well as by high-resolution mass spectrometry (HR-MS) (see ESI).

## 2.2. Thermal stability

The thermal properties of these new small molecules were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) under an inert atmosphere. Thermogravimetric analysis (TGA) was performed to evaluate the stability of these HTMs (Fig. 2). The corresponding data are summarized in Table 1.

The thermal properties of these small molecules were investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) under an inert atmosphere. DMPA(Ph)Pent, DMPA(Ph)₂Pent, DMPA(Ph)₃Pent and Cz(Ph)Pent displayed good thermal stability in TGA tests with 5 % weight loss estimated with 5 % weight loss at 400, 421, 410 °C and 470 °C respectively (Fig. 2). However, by replacing

<figure><img src="image_6.png" /><figcaption>**Fig. 2.** TGA curves of the compounds at 10 °C. min⁻¹ under nitrogen.</figcaption></figure>
<table><caption>**Table 1**
Summary of Thermal and Optical-Electrochemical properties of the HTMs.</caption><thead><tr><th>HTM</th><th>T<sub>d</sub><sup>a</sup><br>(°C)</th><th>T<sub>g</sub><sup>b</sup><br>(°C)</th><th>λ<sub>max</sub> (Exp)<sup>c</sup><br>(nm)</th><th>λ<sub>max</sub> (DFT)<sup>d</sup><br>(nm)</th><th>HOMO - LUMO gap<sup>e</sup><br>(eV)</th><th>E<sub>HOMO/LUMO</sub><sup>f,g</sup><br>(eV)</th><th>E<sub>HOMO</sub> film<sup>h</sup><br>(eV)</th></tr></thead><tbody><tr><td>DMPA(Ph)Pent</td><td>400</td><td>125</td><td>310-325</td><td>287.3</td><td>1.92</td><td>-4.90/-3.00</td><td>-5.30</td></tr><tr><td>DMPA(Ph)<sub>2</sub>Pent</td><td>421</td><td>191</td><td>307/340</td><td>286.7</td><td>1.97</td><td>-5.04/-3.07</td><td>-5.35</td></tr><tr><td>DMPA(Ph)<sub>3</sub>Pent</td><td>410</td><td>231</td><td>307/360</td><td>297.9</td><td>1.98</td><td>-5.11/-3.13</td><td>-5.38</td></tr><tr><td>Cz(Ph)Pent</td><td>470</td><td>212</td><td>307</td><td>309.5</td><td>1.98</td><td>-4.80/-2.82</td><td>-5.15</td></tr></tbody></table>

a 5 % weight loss in TGA.

b DSC data recorded under an N₂ atmosphere at a heating rate of 10 °C.min⁻¹.

c UV-vis spectral data measured in DCM solution.

d UV-vis spectral data calculated by DFT (ωb97xd/6-311G(d,p)) in DCM solution.

e Optical HOMO - LUMO gap = 1240/λ-onset.

f Using cyclic voltammetry (CV) in DCM solution E<sub>HOMO</sub> = -(E<sub>onset</sub> vs. Fc/Fc⁺ + 4.8) eV.

g LUMO value calculated using the relation E<sub>LUMO</sub> = E<sub>g</sub> + E<sub>HOMO</sub>.

h The oxidation potential measured by photoelectron spectroscopy in air (PESA).

dimethoxydiphenylamine by carbazole-DMPA derivative, significantly improves the T<sub>d</sub> by 70 °C. Indeed, this results is probably due to the tridimensional and flexible structure of the DMPA moiety, compared to the conjugated and planar carbazole, which increases the T<sub>d</sub> and consequently improves the stability [31]. A pentacene derivative, TIPS-pentacene, was reported by S. Ahmad et al. for its application as hole transporting material in photovoltaic solar cells. [27] TIPS-pentacene displayed thermal stability up to 380 °C, which is lower in comparison to the materials presented in our study, which demonstrate stability below 400 °C, and significantly lower than Cz(Ph)Pent, which extents thermal stability at 470 °C, indicating superior thermal stability.

Differential scanning calorimetry (DSC) measurements were performed from ambient temperature to 300 °C and demonstrated that DMPA(Ph)Pent, DMPA(Ph)<sub>2</sub>Pent, DMPA(Ph)<sub>3</sub>Pent and Cz(Ph)Pent were naturally in amorphous phases, with glass transition temperatures (T<sub>g</sub>) observed at 125, 191, 231 and 212 °C respectively. Interestingly, increasing the length of the spacer and replace the DMPA by carbazole-DMPA arm results in both cases a significant increase of rigidity. (Fig. S12, ESI) [38].

## 2.3. Photophysical and electrochemical properties

Fig. 3 shows the normalized UV-vis absorption of four small molecules in dichloromethane. All derivatives show a first absorption band around 340–360 nm, attributed to a π-π* transition of the carbazole and diphenylamine moieties [39]. An additional shoulder centered at 380 nm, was monitored for DMPA(Ph)<sub>2</sub>Pent and DMPA(Ph)<sub>3</sub>Pent upon

addition of a second and third phenyl, probably due to a n-π* transition. In the solid state, a broadening of the bands and a hypochromic effect are observed (Fig. S13 ESI), which are thought to be related to the increase in π-π* intermolecular interactions. The last transition was followed by three successive bands at 525, 550, and 600 nm respectively, correspond to the first singlet exciton excitation of pentacene to an unoccupied molecular orbital [40]. Optical band gaps were calculated from solution and give 1.92, 1.97, 1.98 and 1.98 eV respectively for DMPA(Ph)Pent, DMPA(Ph)<sub>2</sub>Pent, DMPA(Ph)<sub>3</sub>Pent and Cz(Ph)Pent, indicating that the additional phenyl units (at least 2) of the spacer or the additional carbazole moiety does not play a role in the band gap determination. The analyzes agreed to DFT.

HOMO levels were determined from the cyclic voltammograms (CV) plotted in Fig. 4, using the relation E<sub>HOMO</sub> = -(E<sub>onset</sub> vs. Fc/Fc⁺ + 4.8) eV [41], using Fc/Fc⁺ as an internal standard. As shown in Fig. 4, the four cyclic voltammograms of the molecules shows a quasi-reversible redox behavior. The DMPA(Ph)Pent, DMPA(Ph)<sub>2</sub>Pent, DMPA(Ph)<sub>3</sub>Pent present one quasi-reversible electron oxidation and assigned to the diphenylamine moieties. Cz(Ph)Pent present two quasi-reversible electron oxidation processes and assigned probably to the formation of the stable radical cation and dication species of carbazole [32]. The onset of the first oxidation potential, were 0.10, 0.24, 0.31, and -0.01 V (vs. Fc/Fc⁺) for DMPA(Ph)Pent, DMPA(Ph)<sub>2</sub>Pent, DMPA(Ph)<sub>3</sub>Pent and Cz(Ph)Pent with values of -4.90, -5.04, -5.11 eV for DMPA(Ph)Pent, DMPA(Ph)<sub>2</sub>Pent, DMPA(Ph)<sub>3</sub>Pent and Cz(Ph)Pent respectively. Therefore, using the formula E<sub>HOMO</sub> = -(E<sub>onset</sub> vs. Fc/Fc⁺ + 4.8) eV, with Fc/Fc⁺ as internal standard, the calculated HOMO levels are estimated to be -4.90, -5.04, -5.11 and -4.80 eV for DMAP(Ph)Pent, DMPA(Ph)<sub>2</sub>Pent, DMPA(Ph)<sub>3</sub>Pent and Cz(Ph)Pent respectively. As shown in Fig. 4, the electron transfer of DMPA(Ph)Pent is observed at a low oxidation potential (0.097 V), while that of DMPA(Ph)<sub>2</sub>Pent is 0.24 V and DMPA(Ph)<sub>3</sub>Pent which oxidized at 0.31 V. It can be seen that increasing the length of spacer effectively weakens the electron-donating effect of arylamine moieties resulting in higher oxidation potentials and stabilization of the HOMO levels of the HTM. This effect has already been reported in the literature on an anthracene π-linked and showing that the addition of one phenyl spacer between the anthracene core and the DMPA arms leading to decreases the HOMO level, which indicates that the benzene ring spacer weakens the electron-donating effect of arylamine moieties. [42] This trend was also confirmed, in solid state, by photoemission spectroscopy in air (PESA) measurements (Table 1 and Fig. S14) which would be beneficial to the hole extraction once embedded in devices. Moreover, these data indicate that the use of carbazole-DMPA unit, more electron-donating groups instead of DMPA, significantly decrease the oxidation potential of the HTM (-0.01 V) and increase the HOMO level of molecule, due to an extension of the π-conjugated system and increasing of the electronic delocalization of the molecules.

<figure><img src="image_7.png" /><figcaption>Fig. 3. The normalized UV-Vis spectra of the compounds in dichloromethane.</figcaption></figure>
<figure><img src="image_8.png" /><figcaption>Fig. 4. Voltammograms of compounds (10⁻³ mol. l⁻¹) at 50 mV.s⁻¹ in a dichloromethane/ tetrabutylammonium perchlorate electrolyte (0.1 mol. l⁻¹).</figcaption></figure>

### 3. Theoretical calculations

In order to better understand the electronic, optical and redox properties of this new family of pentacene derivative, extensive density functional theory (DFT) calculations were performed and computed using Gaussian 09. All geometry optimizations were performed using density functional theory (DFT) with the global hybrid exchange-correlation functional ωb97xd and basis set (6-311G(d,p)). All the calculations were performed taking into consideration dichloromethane as the solvent. The geometries and energies of different compounds were determined at different levels of calculations (see ESI part 4).

The experimental results were compared with those obtained by molecular modelling. The modelling parameters are described in supporting information. The optimized geometries (shown in Fig. 5) show that the phenyls spacer are not planar to the pentacene core.

The dihedral angles between pentacene and phenyl are given below the name of the molecule. This later between the pentacene core and the first phenyl are between 81.6 and 100.1° for all molecules. This angle around 90° can be explained by the repulsion of the H of pentacene core and phenyl spacer. As a results, these non-planar configurations do not favor the electron delocalization between the pentacene core and DMPA or Cz arms [43].

Fig. 6. Shows that the profiles of the simulated spectra are close to

<figure><img src="image_9.png" /><figcaption>Fig. 6. Theoretical UV-visible absorption spectra of target molecules.</figcaption></figure>

the experimental spectra. Similarly, the comparison of the maximum wavelengths reported in Table 1 shows that these theoretical and experimental values are very close (difference of less than 25 nm). These similarities allow us to validate the use of ωB97XD functional

<figure><img src="image_10.png" /><figcaption>Fig. 5. Optimized geometries by DFT of pentacene based derivatives.</figcaption></figure>
in DFT modelling. The main difference between the simulated and experimental spectra is that many transitions are observed in the experimental spectra as opposed to the theoretical spectra. For example, in the region between 500 and 650 nm, 3 transitions are easily observed, whereas only one transition is observed in the theoretical spectra. This significant difference can be explained by the fact that the simulated spectrum only considers the optimized configuration of Fig. 3, whereas the solution contains many possible configurations with very close energies. These configurations result probably from the rotation of the end groups as DMPA arms. The assignment of transitions around 550 nm corresponds to the HOMO → LUMO transition for DMPA(Ph)nPent family and to the HOMO-2 → LUMO transition for Cz(Ph)Pent. According to the molecular orbital diagrams (Fig. S16), the HOMO → LUMO transition of DMPA(Ph)nPent corresponds to a π-π* transition within the pentacene group. Similarly, the HOMO-2 → LUMO transition of Cz(Ph)Pent corresponds to a π-π* transition within the pentacene core.

The absorptions around 300 nm correspond mainly to transitions within a same group (Table 2). Some transitions involve phenyls, especially for DMPA(Ph)₂Pent. For Cz(Ph)Pent these transitions correspond only to transitions within the carbazole. None of the main absorptions corresponds at pentacene to DMPA or carbazole transitions. The presence of a phenyl is sufficient to prevent transitions between pentacene cores to DMPA or carbazole arms.

The energy levels corresponding to the π-π* transition in pentacene core, determined experimentally and by DFT, are shown at Fig. 7.

It can be seen that the difference between the levels is either overestimated by the DFT calculations or underestimated by the experiments. However, these energy differences are in agreement with each other (Table 3). The difference for DMPA(Ph)Pent is slightly smaller than for the other 3 molecules which have the same energy difference. The transition within the pentacene is therefore not affected (or very little in the case of DMPA(Ph)Pent by the number of phenyl groups between the pentacene and the DMPA and carbazole groups. In fact, the orientation of the first phenyl with respect to the pentacene limits electron delocalization between the pentacene core and DMPA or Cz arms. Similarly, the nature of the terminal group (DMPA or carbazole) has very little influence on this transition.

Taken together, these results confirm that the presence of a phenyl group allows the electron transfer between the pentacene and the DMPA and carbazole groups to be annihilated. These results are also consistent with the non-planar geometries of these molecules.

# 4. Experimental section

## 4.1. General methods

An Anton Paar Monowave 300 micro-wave reactor was used for organic synthesis. NMR spectra were recorded on a Bruker Avance 300

<table><caption>**Table 2**

Assignation of the maximum absorption at the MO transition and groups affect</caption><thead><tr><th>Molecules</th><th>λ<sub>theo</sub> (nm)</th><th>MO transitions</th><th>Groups transition</th></tr></thead><tbody><tr><td rowspan="2">DMPA(Ph)Pent</td><td>287,3</td><td>HOMO-6 → LUMO</td><td>Pent → Pent</td></tr><tr><td>285,7</td><td>HOMO → LUMO+2</td><td>Pent → Pent + (Ph)</td></tr><tr><td rowspan="2">DMPA(Ph)₂Pent</td><td>301,4</td><td>HOMO-2 → LUMO+5</td><td>DMPA → Ph</td></tr><tr><td>297,7</td><td>HOMO-1 → LUMO+5</td><td>DMPA + Ph → DMPA</td></tr><tr><td rowspan="5">DMPA(Ph)₃Pent</td><td>306,5</td><td>HOMO-2 → LUMO+5</td><td>DMPA + Ph → DMPA</td></tr><tr><td>287,1</td><td>HOMO-1 → LUMO+1</td><td>DMPA → Ph</td></tr><tr><td>287,0</td><td>HOMO-3 → LUMO</td><td>DMPA + Ph → Pent</td></tr><tr><td></td><td>HOMO-2 → LUMO</td><td>DMPA + Ph → Pent</td></tr><tr><td></td><td>HOMO-8 → LUMO</td><td>Pent → Pent</td></tr><tr><td rowspan="4">Cz(Ph)Pent</td><td>338,8</td><td>HOMO → LUMO+4</td><td>Pent → Pent</td></tr><tr><td>338,3</td><td>HOMO-3 → LUMO+2</td><td>Cz → Cz</td></tr><tr><td>309,8</td><td>HOMO-4 → LUMO+1</td><td>Cz → Cz</td></tr><tr><td>309,5</td><td>HOMO → LUMO+1</td><td>Cz → Cz</td></tr><tr><td></td><td></td><td>HOMO-1 → LUMO+2</td><td>Cz → Cz</td></tr></tbody></table>

<figure><img src="image_11.png" /><figcaption>**Fig. 7.** Comparison of the energy levels corresponding to absorptions around 550 nm determined by experimental measurements and by DFT calculations in dichloromethane. Note: the π-π* transition correspond to the HOMO-2 → LUMO transition for the Cz(Ph)Pent.</figcaption></figure>

<table><caption>**Table 3**

Comparison of ΔE corresponding to absorptions around 550 nm determined by experimental measurements and by DFT calculations in DCM.</caption><thead><tr><th>Molecule</th><th>ΔE<sub>Exp</sub> (eV)</th><th>ΔE<sub>DFT</sub> (eV)</th></tr></thead><tbody><tr><td>DMPA(Ph)Pent</td><td>1.90</td><td>2.24</td></tr><tr><td>DMPA(Ph)₂Pent</td><td>1.97</td><td>2.26</td></tr><tr><td>DMPA(Ph)₃Pent</td><td>1.98</td><td>2.26</td></tr><tr><td>Cz(Ph)Pent</td><td>1.98</td><td>2.26</td></tr></tbody></table>

(300 MHz) spectrometer. UV-vis spectra were recorded with a Jasco V-670 spectrometer. Differential scanning calorimetry (DSC) measurements were performed on Perkin-Elmer DSC-400 (heating/cooling rate 5 °C.min⁻¹). Thermogravimetric analysis (TGA) was fulfilled using a Perkin Elmer STA 6000 at a heating rate of 10 °C.min⁻¹ under N₂. Cyclic voltammetry was performed on a Biologic Applied Research MPG2 multi-channel potentiostat, in a 10⁻³ mol.L⁻¹ solution with 0.1 M tetra-butylammoniumperchlorate (TBAP) in dichloromethane as supporting electrolyte at a scan rate of 50 mV.s⁻¹ in a three-electrode cell, the working electrode, the reference and the counter electrode are respectively a platinum disc (1 cm in diameter), two platinum wires, one of which is a pseudo reference.

## 4.2. Materials and reagents

All starting materials were purchased and used without further purification. 4,4-dibromophenyl, SnCl₂ dihydrate, tris(dibenzylideneacetone)dipalladium, Palladium (II) acetate, P(tBu)₃, K₂CO₃, petroleum ether, dichloromethane, Et₂O, toluene, dry THF, methanol and chloroform were purchased from Fisher scientific. Bis (4-methoxyphenyl) amine was purchased from Ikamba organics. n-Butyllithium (2.5 M in cychlohexane), NaOtBu and tetrakis (triphenylphosphine) palladium, DMF (anhydrous), DMSO (anhydrous) were purchased from Sigma Aldrich.

### 4.2.1. Synthesis of (PhBr)₂Pent

4,4-dibromophenyl (3g, 0, 0132 mol) was dissolved under nitrogen in dry THF (60 mL). After dissolution, the mixture was cooled to -78 °C and 4.9 ml of n-Butyllithium (2.5 M in cychlohexane) was added dropwise. The mixture was stirred at -78 °C for 30 min. 6,13-Pentacenequione (0.7 g, 0.0022 mol) was then added and the mixture was stirred at -78 °C for 1 h followed by 2 h at room temperature (all solids disappeared, and solution became dark brown). 18 ml 10 % HCl aqueous solution saturated with SnCl₂ dihydrate was added dropwise in absence
of light. This mixture was refluxed for 1 h and then allowed to cool to room temperature. The deep blue precipitate formed was filtered, washed with methanol and dissolved in chloroform. The combined organic layer was dried with anhydrous MgSO₄ and evaporated to dryness to yield the desired compound as a blue solid (0.9g, 69%). ¹H NMR (300 MHz, CDCl₃) δ (ppm): 8.27 (s, 4H), 7.87 (d, J = 8.3 Hz, 4H), 7.75 (dd, J = 6.6, 3.2 Hz, 4H), 7.51 (d, J = 8.2 Hz, 4H), 7.26 (s, 4H). ¹³C NMR spectra were not obtained due to limited solubility in common solvents. HRMS (MALDI-TOF): M⁺: 587.99142 (calculated m/z 588.33 g).

### 4.2.2. Synthesis of DMPA(Ph)Pent

6, 13-bis (4-bromophenyle) pentacene (0.7 g, 0.0012 mol), bis(4-methoxyphenyl)amine (1.1g, 0.005 mol), NaOtBu (0.54g, 0.006 mol) and Pd₂dba₃ (0.1g, 0.00018 mol) were added into a Schlenk tube and vacuumed for 10 min. Afterwards, anhydrous toluene (30 ml) and P(tBu)₃ (0.26g, 0.001 mol) were added and the mixture was vacuumed and degassed for 20 min. Subsequently, the reaction was stirred under reflux for 24h. After the reaction mixture was cooled to room temperature, the organic solution was diluted with water and extracted with dichloromethane. The organic layer was washed with a saturated solution of NaCl then dried over anhydrous MgSO₄. The solvent was evaporated under reduce pressure and the crude product was purified by silica gel column chromatography using a mixture of petroleum ether/dichloromethane (1/1) as eluent. The solvent was evaporated under reduce pressure then the product was precipitated using a mixture of Et₂O/THF (5/1) to yield the desired compound as a blue solid (0.5g, 48%). ¹H NMR (300 MHz, d8) δ (ppm): 8.48 (s, 4H), 7.78 (dd, J = 6.6 Hz, 3.2 Hz, 4H), 7.38 (d, J = 8.6 Hz, 4H), 7.34 - 7.26 (m, 8H), 7.26 - 7.17 (m, 8H), 7.03 - 6.89 (m, 8H), 3.80 (s, 12H). ¹³C NMR (75 MHz, d8) δ (ppm): 157.44, 149.31, 141.47, 137.59, 132.86, 131.81, 131.30, 129.85, 129.17, 127.93, 126.32, 125.54, 119.78, 115.47, 5543. HRMS (MALDI-TOF): M⁺: 884.36086 (calculated m/z 884.36)

### 4.2.3. Synthesis of DMPA(Ph)₂Pent

6, 13-bis (4-bromophenyle) pentacene (0.1 g, 0.0002 mol), N₃,N₃,N₆, N₆-tetrakis-(4-methoxyphenyl)-9H-carbazole-3,6-diamine (0.265g, 0.0004 mol), NaOtBu (0.05g, 0.0006 mol) and Pd(OAc)₂ (6 mg, 0.00002 mol) were added into a Schlenk tube and vacuumed for 10 min. Afterwards, anhydrous toluene (30 ml) and P(tBu)₃ (0.04 ml, 0.00016 mol) was added and the mixture was vacuumed and degassed for 20 min. Subsequently, the reaction was stirred at reflux for 24h. After the reaction mixture was cooled to room temperature, it was filtered through a celite pad, rinsed with THF and evaporated under reduce pressure. The product was precipitated using a mixture of Et₂O/toluene (5/1) to yield the desired compound as a blue solid (58 mg, 35%). ¹H NMR (300 MHz, d8) δ (ppm): 8.55 (s, 4H), 8.06 (d, J = 7.8 Hz, 4H), 7.95 (d, J = 7.3 Hz, 4H), 7.85 (dd, J = 5.7, 3.4 Hz, 4H), 7.79 (s, 4H), 7.70 (d, J = 7.4 Hz, 4H), 7.25 (dd, J = 11.8, 3.7 Hz, 8H), 7.00 (d, J = 7.8 Hz, 16H), 6.79 (d, J = 7.3 Hz, 16H), 3.74 (s, 24H). ¹³C NMR spectra were not obtained due to limited solubility in common solvents. M⁺: 1668. 66, 582 (calculated m/z 1669.95).

### 4.2.4. Synthesis of DMPA(Ph)₃Pent

6, 13-bis (4-bromophenyle) pentacene (0.6 g, 0.001 mol, 1 eq), 4-methoxy-N-(4-methoxyphenyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2 yl) phenyle) aniline (1.43g, 0.003 mol) and K₂CO₃ (1.3g, 0.003 mol) were added into a Schlenk tube and vacuumed for 10 min. A mixture of dry toluene (12 mL), dry THF (12 mL) and water (6 mL) was added and degassed for 20 min, then the mixture was mixed was stirred at 60 °C. Tetrakis (triphenylphosphine) palladium (0.2g, 0.00015 mg) was introduced and the mixture was stirred at 100 °C for 24h. After, the organic solution was diluted with water and extracted with dichloromethane. The organic layer was washed with a saturated solution of NaCl then dried over anhydrous MgSO₄. The solvent was evaporated, and the crude product was purified by silica gel column chromatography with a mixture of dichloromethane/petroleum ether (7/3) as eluent. The

solvent was evaporated under reduce pressure, the product was then precipitated in a mixture of Et₂O/THF (5/1) to yield the desired compound as a purple solid (0.47g, 45%). ¹H NMR (300 MHz, d8) δ (ppm): 8.44 (s, 4H), 7.99 (d, J = 8.1 Hz, 4H), 7.76 (dd, J = 9.2, 2.6 Hz, 6H), 7.72 - 7.65 (m, 6H), 7.21 (dd, J = 6.8, 3.0 Hz, 4H), 7.12 (d, J = 8.9 Hz, 8H), 7.06 (d, J = 8.6 Hz, 4H), 6.90 (d, J = 8.9 Hz, 8H), 3.79 (s, 12H). ¹³C NMR (75 MHz, d8) δ (ppm): 157.20, 149.33, 141.58, 140.90, 138.45, 137.55, 133.34, 132.94, 131.99, 129.49, 128.95, 127.98, 127.40, 127.03, 125.96, 125.70, 121.15, 115.35, 55.42. HRMS (MALDI-TOF): M⁺: 1036.42 (calculated m/z 1037.25).

### 4.2.5. Synthesis of Cz(Ph)Pent

13-bis (4-bromophenyle) pentacene (0.6 g, 0.001 mol), de N, N-bis (4-methoxyphenyl)-4'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl]-4-amine (1.5g, 0.003 mol), and K₂CO₃ (1.3g, 0.008 mol) were added into a Schlenk tube and vacuumed for 10 min. A mixture of dry toluene (20 mL), dry THF (12 mL) and water (4 mL) were added and the mixture was mixed was stirred at 60 °C. Then, tetrakis (triphenylphosphine) palladium (0.2g, 0.00015 mg) was introduced and the mixture was stirred at 100 °C for 24h. After, the reaction mixture was cooled to room temperature, filered on through a celite pad, rinsed with THF and evaporated under reduce pressure. The product was precipitated with a mixture of Cyclohexane/Toluene (5/1) to yield the desired compound as a blue solid (0.27g, 22%). ¹H NMR (300 MHz, d8) δ (ppm): 8.46 (s, 4H), 8.11 (d, J = 7.9 Hz, 4H), 7.96 (d,d, J = 7.9 Hz, 4H), 7.85 - 7.72 (m, 12H), 7.59 (d, J = 8.6 Hz, 4H), 7.22 (dd, J = 6.8, 2.8 Hz, 4H), 7.08 (d, J = 8.3 Hz, 8H), 7.01 (d, J = 8.5 Hz, 4H), 6.87 (d, J = 8.7 Hz, 8H), 3.77 (s, 12H). ¹³C NMR spectra were not obtained due to limited solubility in common solvents. HRMS (MALDI-TOF): M⁺: 1188.486 (calculated m/z 1189.44).

## 5. Conclusion

Four novel thermally stable and soluble compounds, constituted by a pentacene core and DMPA/carbazole-DMPA arms, have been designed, synthesized using various phenyl spacers, and thoroughly characterized. These new developed molecules display good solubility in common solvents, approving that the incorporation of DMPA and carbazole-DMPA arms effectively addresses solubility challenges. A structure-property relationship has been established, focusing on two parameters. The effect of extending the phenyl spacer length is evident in the following observations: Increasing the number of phenyl units within the spacer enhances the rigidity of the molecules, with the highest T<sub>g</sub> value recorded at 231 °C for DMPA(Ph)₃Pent. ii) The HOMO energy level, determined through electrochemical and PESA measurements, is improved by increasing the phenyl spacer length. In parallel, the replacement of DMPA arms with carbazole-DMPA moieties results in several key improvements: i) The thermal decomposition temperature (T<sub>d</sub>) is improved, indicating better thermal stability, with Cz(Ph)Pent exhibiting a T<sub>d</sub> of 470 °C, compared to 400 °C for DMPA(Ph)Pent. ii) The glass transition temperature (T<sub>g</sub>) is also increased due to the introduction of the rigid and planar carbazole building-block, with Cz(Ph)Pent attainment 212 °C, in compare to the 125 °C observed for DMPA(Ph)Pent. iii) The HOMO energy level, as determined by electrochemical and PESA measurements, is high due to the extended π-conjugation and improved electronic delocalization in the carbazole-substituted arms (−4.80 eV for Cz(Ph)Pent versus -4.90 eV for DMPA(Ph)Pent). The experimental results are supported by density functional theory (DFT) calculations, which provided optimized geometries, molecular orbital energies, theoretical absorption spectra and the assignment of the main electronic transitions. The combination of facile synthetic accessibility, high thermal stability and rigidity, promising electrochemical properties, coupled with good solubility and the integration of methoxy groups, present significant potential for a range of applications as will organic electronics devices or for use as interface layers in perovskite solar cells.
CRediT authorship contribution statement

**Zeinab Kadi:** Writing – original draft, Methodology, Investigation, Conceptualization, Formal analysis. **Sebastien Peralta:** Writing – review & editing, Formal analysis. **Clément Cabanetos:** Formal analysis. **Marwan Kobeissi:** Supervision. **Bruno Schmaltz:** Supervision, Resources, Conceptualization.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This research was funded by the CERTeM 5.0 Program through the grant MASOFLEX and the financial support of the Regional council Centre-Val-De-Loire through the grant ETHERMO.

Supplementary materials

Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.molstruc.2025.141701.

Data availability

Data will be made available on request.

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