Caroline Fradin

Frédéric Guittard

Igor F Perepichka
email: i.perepichka@bangor.ac.uk

Thierry Darmanin
email: thierry.darmanin@univ-cotedazur.fr

Soft-template electropolymerization of 3,4-(2,3-naphtylenedioxy)thiophene-2acetic acid esters favoring dimers: Controlling the surface nanostructure by side ester groups

Keywords: Electropolymerization, Surface nanostructures, Template, Hydrophobicity, Conjugated polymers

A series of the esters of 3,4-(2,3-naphtylenedioxy)thiophene-2-acetic acid (NaphDOT-R) have been synthesized, with varying the structure of the ester fragments in the molecules (fluoroalkyl groups and different aromatic moieties: benzene, naphthalene, carbazole and pyrene). Their anodic oxidation by cyclic voltammetry scanning between -1 and +2.0 V led to electrochemical deposition of the films on the electrode surface which show different surface morphology. NaphDOT-R derivatives can be divided into two groups: (1) the monomers with fluoroalkyl and benzyl ester groups can only dimerize with depositing insoluble dimers on the electrode surface, whereas (2) monomers with condensed aromatic moieties (naphthalene, carbazole and pyrene) in the ester fragment undergo further electropolymerization involving these groups. The surfaces of the deposited films were studied by scanning electron microscopy toward their roughness and wettability. The influence of water on the electropolymerization process and the surface nanostructures is discussed through TEM observations of the micellar template in the electropolymerization solutions. No template was nevertheless detected for NaphDOT-Pyr in dichloromethane, which electropolymerization leads to the formation of aggregated spherical nanoparticles or tree-like surface nanostructures (3D), whereas in dichloromethane saturated with water, unidirectional (1D) growth of vertically aligned nanotubes was observed. The wettability studies on electrodeposited films with three probe liquids (water diiodomethane and hexadecane) showed that they are generally slightly hydrophobic and oleophilic, while the structure of the side ester group and the deposition conditions effect on the quantitative parameters of the surface roughness and wettability.

Introduction

Polythiophenes and thiophene-based conjugated molecular systems, oligomers and copolymers represent fascinating class of materials widely used in materials science [START_REF]Handbook of Thiophene-Based Materials: Applications in Organic Electronics and Photonics[END_REF], especially in various fields of organic electronics and optoelectronics: organic photovoltaics (OPV) [START_REF] Yu | Conjugated polymers for photon-to-electron and photon-to-fuel conversions[END_REF][START_REF] Cui | Organic photovoltaic cells for indoor applications: opportunities and challenges[END_REF], organic lightemitting diodes (OLED) [START_REF] Perepichka | Light emitting polythiophenes[END_REF], organic field-effect transistors (OFET) [START_REF] Nielsen | Recent advances in transistor performance of polythiophenes[END_REF][START_REF] Baeg | Toward printed integrated circuits based on unipolar or ambipolar polymer semiconductors[END_REF][START_REF] Larik | Thiophene-based molecular and polymeric semiconductors for organic field effect transistors and organic thin film transistors[END_REF], electrically conductive layers [START_REF] Bert" Groenendaal | Poly(3,4ethylenedioxythiophene) and its derivatives: Past, present, and future[END_REF][START_REF] Elschner | Principles and applications of an intrinsically conductive polymer[END_REF], hole transporters [START_REF] Kundu | Hydrophobic polythiophene hole-transport layers to address the moisture-induced decomposition problem of perovskite solar cells[END_REF][START_REF] Ma | Spiro-thiophene derivatives as hole-transport materials for perovskite solar cells[END_REF], electrochromics (EC) [START_REF] Beaujuge | Color control in π-conjugated organic polymers for use in electrochromic devices[END_REF][START_REF] Amb | Navigating the color palette of solution-processable electrochromic polymers[END_REF][START_REF] Zhu | Molecular engineering tuning optoelectronic properties of thieno[3,2b]thiophenes-based electrochromic polymers[END_REF][START_REF] Beverina | Multichromophoric electrochromic polymers: colour tuning of conjugated polymers through the side chain functionalization approach[END_REF], batteries [START_REF] Novák | Electrochemically active polymers for rechargeable batteries[END_REF][START_REF] Aradilla | All-polythiophene rechargeable batteries[END_REF],

supercapacitors [START_REF] Wu | Sulfur/polythiophene with a core/shell structure: synthesis and electrochemical properties of the cathode for rechargeable lithium batteries[END_REF][START_REF] Liu | Dioxythiophene-based polymer electrodes for supercapacitor modules[END_REF][START_REF] Zhang | A high-performance supercapacitor based on a polythiophene/multiwalled carbon nanotube composite by electropolymerization in an ionic liquid microemulsion[END_REF], sensors [START_REF] Li | Polythiophene-based optical sensors for small molecules[END_REF][START_REF] Chan | Thermoresponsive laterally-branched polythiophene phenylene derivative as water-soluble temperature sensor[END_REF] etc.

One straightforward method of synthesis of polythiophenes is an electropolymerization of corresponding thiophene monomers that allows quick access to conjugated polymers and study their properties. Polythiophenes obtained by electropolymerization technique form films, the morphology and surface nanostructure of which substantially depend (apart of other factors) on the structure of used thiophene building blocks. This approach attracts an interest in a surface science, for modification of surfaces to create the nanostructures and to bring hydrophobic, parahydrophobic or superhydrophobic properties to the surface [START_REF] Darmanin | Wettability of conducting polymers: from superhydrophilicity to superoleophobicity[END_REF][START_REF] Bellanger | Chemical and physical pathways for the preparation of superoleophobic surfaces and related wetting theories[END_REF][START_REF] Darmanin | Superhydrophobic surfaces by electrochemical processes[END_REF]. Controlling the surface nanostructure, hydrophobicity and water or oil adhesion is a challenging task for many technological applications, including antifouling and self-cleaning surfaces [START_REF] Yu | Biomimetic transparent and superhydrophobic coatings: from nature and beyond nature[END_REF][START_REF] Darmanin | Recent advances in the potential applications of bioinspired superhydrophobic materials[END_REF], water/fog harvesting [START_REF] Dong | Superoleophobic slippery lubricant-infused surfaces: combining two extremes in the same surface[END_REF][START_REF] Ju | A multi-structural and multi-functional integrated fog collection system in cactus[END_REF], microfluidic systems [START_REF] Wasay | Gecko gaskets for self-sealing and high-strength reversible bonding of microfluidics[END_REF][START_REF] Popova | Dropletarray (DA) sandwich chip: a versatile platform for high-throughput cell screening based on superhydrophobic-superhydrophilic micropatterning[END_REF], and micropatterning [START_REF] Popova | Dropletarray (DA) sandwich chip: a versatile platform for high-throughput cell screening based on superhydrophobic-superhydrophilic micropatterning[END_REF][START_REF] Geyer | Superhydrophobic-superhydrophilic micropatterning: towards genome-on-a-chip cell microarrays[END_REF].

One of the advantages of electropolymerization technique [START_REF] Waltman | Electrically conducting polymers: a review of the electropolymerization reaction, of the effects of chemical structure on polymer film properties, and of applications towards technology[END_REF][START_REF]Electropolymerization: Concepts, Materials and Applications[END_REF][START_REF]Handbook of Electropolymerization[END_REF] is that the process is very fast while the obtaining of ordered porous structures is possible with a process called templateless electropolymerization (soft-template electropolymerization) [START_REF] Darmanin | Superhydrophobic surfaces by electrochemical processes[END_REF][START_REF] Sane | Coral-like nanostructures[END_REF]. A soft template is a non-rigid template but uses as it that means, here, to force the electropolymerization around the soft template but not inside. The soft templates include gas bubbles as well as micelles in solution.

For example, the electropolymerization of pyrrole directly in water leads to ordered porous structures as microcontainers and microtubules [START_REF] Qu | Electrochemical growth of polypyrrole microcontainers[END_REF][START_REF] Fakhry | Mechanism of formation of templateless electrogenerated polypyrrole nanostructures[END_REF][START_REF] Debiemme-Chouvy | Electrosynthesis of polypyrrole nano/micro structures using an electrogenerated oriented polypyrrole nanowire array as framework[END_REF][START_REF] Mccarthy | Electrochemical deposition of hollow N-substituted polypyrrole microtubes from an acoustically formed emulsion[END_REF]. The process involves gas bubbles (O2 and or H2) formation from water (H2O) which are released on the substrate during the electropolymerization process acting as soft template and facilitating the polymer growth as ordered structures on the surface. In this case, surfactants are often used to stabilize the gas bubbles and induce the polymerization around them, while in some cases this process of ordered structures formation can be realized in organic solvents and without surfactant subject the traces of water are present in solution [START_REF] Luo | Polydioxythiophene nanodots, nanowires, nano-networks, and tubular structures: the effect of functional groups and temperature in template-free electropolymerization[END_REF][START_REF] Chagas | One-step and templateless electropolymerization process using thienothiophene derivatives to develop arrays of nanotubes and tree-like structures with high water adhesion[END_REF][START_REF] Darmanin | A One-step electrodeposition of homogeneous and vertically aligned nanotubes with parahydrophobic properties (high water adhesion)[END_REF][START_REF] Fradin | Micellar formation by soft template electropolymerization in organic solvents[END_REF][START_REF] Szczepanski | A template-free approach to nanotube-decorated polymer surfaces using 3,4-phenylenedioxythiophene (PhEDOT) monomer[END_REF].

Poly- (3,4-ethylenedioxythiophene) (PEDOT) is one of the most studied conducting polymers, with low oxidation potential, a highly stable oxidized state, and exceptional electronic properties [START_REF] Bert" Groenendaal | Poly(3,4ethylenedioxythiophene) and its derivatives: Past, present, and future[END_REF][START_REF] Elschner | Principles and applications of an intrinsically conductive polymer[END_REF][START_REF] Kirchmeyer | Scientific importance, properties and growing applications of poly(3,4-ethylenedioxythiophene)[END_REF]. Large number of functionalized PEDOTs (prepared form substituted EDOT monomers or through copolymerization of EDOT with other monomer building blocks) have been reported in the literature [START_REF] Roncali | 3,4-Ethylenedioxythiophene (EDOT) as a versatile building block for advanced functional π-conjugated systems[END_REF]. Electrochemically deposited films of functionalized PEDOTs have been shown to form various nanostructures on a surface, structures and hydrophobicity of which can be controlled by side-chain functionalization [START_REF] Luo | Perfluoro-functionalized PEDOT films with controlled morphology as superhydrophobic coatings and biointerfaces with enhanced cell adhesion[END_REF][START_REF] Darmanin | Hydrocarbon versus fluorocarbon in the electrodeposition of superhydrophobic polymer films[END_REF][START_REF] Wolfs | Superhydrophobic nanofiber arrays and flower-like structures of electrodeposited conducting polymers[END_REF][START_REF] Darmanin | Superoleophobic surfaces with short fluorinated chains?[END_REF][START_REF] Godeau | Switchable surfaces from highly hydrophobic to highly hydrophilic using covalent imine bonds[END_REF].

The benzene-fused analogue of EDOT, 3,4-phenylenedioxythiophene (PheDOT) (Figure 1) [START_REF] Roquet | 3,4-Phenylenedioxythiophene (PheDOT): a novel platform for the synthesis of planar substituted π-donor conjugated systems[END_REF][START_REF] Perepichka | Electronic properties and reactivity of short-chain oligomers of 3,4-phenylenedioxythiophene (PheDOT)[END_REF], offers a wider range of side-chain functionalization (alkyl or aryl substituents, electrondonating or electron-withdrawing groups at the benzene ring, R-PheDOT) expanding the library of monomers for conducting polymers [START_REF] Grenier | Regiosymmetric poly(dialkylphenylenedioxythiophene)s: electron-rich, stackable π-conjugated nanoribbons[END_REF][START_REF] Poverenov | Flat conjugated polymers combining a relatively low HOMO energy level and band gap: polyselenophenes versus polythiophenes[END_REF][START_REF] Shibasaki | Synthesis and characterization of soluble poly(3,4phenylenedioxythiophene)[END_REF][START_REF] Krompiec | 3,4-Phenylenedioxythiophenes (PheDOTs) functionalized with electronwithdrawing groups and their analogs for organic electronics[END_REF]. It also represents a special interest for softtemplate electropolymerization due to its strong ability to form highly ordered porous nanostructures such as vertically aligned nanotubes, probably due to -stacking interactions favoring the deposition in a preferential direction [START_REF] Fradin | Micellar formation by soft template electropolymerization in organic solvents[END_REF][START_REF] Szczepanski | A template-free approach to nanotube-decorated polymer surfaces using 3,4-phenylenedioxythiophene (PhEDOT) monomer[END_REF]. Electropolymerization of PheDOT derivatives, R-PheDOT, was shown to form rich pallet of surface nanostructures of the polymer films depending on the functional group substitution at the benzene ring [START_REF] Darmanin | A templateless electropolymerization approach to porous hydrophobic nanostructures using 3,4phenylenedioxythiophne monomers with electron-withdrawing groups[END_REF][START_REF] Darmanin | Exceptionally strong effect of small structural variations in functionalized 3,4-phenylenedioxythiophenes on the surface nanostructure and parahydrophobic properties of their electropolymerized films[END_REF]. The naphthalenefused analog of EDOT, 3,4-(2,3-naphtylenedioxy)thiophene (NaphDOT), has proven to be an exceptional monomer for soft-template electropolymerization, forming extremely ordered nanotubular polymeric structures on the electrode surface [START_REF] Darmanin | A One-step electrodeposition of homogeneous and vertically aligned nanotubes with parahydrophobic properties (high water adhesion)[END_REF][START_REF] Fradin | Micellar formation by soft template electropolymerization in organic solvents[END_REF]. [START_REF] Raimundo | Push-pull chromophores based on 2,2'-bi(3,4-ethylenedioxythiophene) (BEDOT) πconjugating spacer[END_REF][START_REF] Turbiez | Stable and soluble oligo(3,4-ethylenedioxythiophene)s endcapped with alkyl chains[END_REF][START_REF] Nalin De Silva | Long-chain 3,4-ethylenedioxythiophene/thiophene oligomers and semiconducting thin films prepared by their electropolymerization[END_REF][START_REF] Conboy | To bend or not to bendare heteroatom interactions within conjugated molecules effective in dictating conformation and planarity?[END_REF] and also confirmed by DFT calculations for oligomers and polymers [START_REF] Poverenov | Flat conjugated polymers combining a relatively low HOMO energy level and band gap: polyselenophenes versus polythiophenes[END_REF][START_REF] Krompiec | 3,4-Phenylenedioxythiophenes (PheDOTs) functionalized with electronwithdrawing groups and their analogs for organic electronics[END_REF]. In addition, PheDOT and especially NaphDOT have expanded π-system bringing hydrophobic properties to the formed polymers, and highly planar rigid structure of their backbone favors -stacking interactions between the polymer chains. The process of growing ordered nanostructures on the surface proceeded well without adding surfactants, and it is believed that the structure of used monomers and formed polymer play crucial role in this case.

We recently show that, as soon as tract water are present in solution, NaphDOT monomers together with electrolytes were forming reverse micelles prior to electropolymerization in organic solvents and that their size corresponded to the electrodeposited nanoporous structures [START_REF] Fradin | Micellar formation by soft template electropolymerization in organic solvents[END_REF]. These reverse micelles act as templates around which polymer films grow on electropolymerization.

In the case of 2-substituted thiophene, electrochemical oxidation to radical cations can only lead to coupling of the monomers giving the dimers, with no further progress of the chain growth to conjugated polymers. When such dimers are badly soluble, they can precipitate from a solution during electrochemical oxidation forming the deposits on the electrode surface. In contrast to extensively studied surface nanostructures from electropolymerized films of conjugated polymers, the deposition of such dimers or short oligomers is under-investigated, with lack of knowledge on the formed surfaces.

Considering exceptional properties of electropolymerized NaphDOT toward soft-template formation of ordered porous structures on a surface, in this work, we investigated electrochemical behavior and the structure of electrodeposited films from a series of its derivatives (1 -7) functionalized at position 2 of the thiophene ring (Figure 2). Side -CH2-C(O)-OR groups have been attached to position 2 of the thiophene ring through CH2 bridge to ensure weak electropositive inductive effect, to not decrease the highest occupied molecular orbital (HOMO) of NaphDOT for its straightforward electrochemical oxidation. As an ester groups, we used electrochemically inactive (in the range of used potentials for electrooxidation) fluoroalkyl or benzyl groups, as well as larger aromatic/heteroaromatic moieties (naphthalene, carbazole, pyrene), which can (potentially) be also involved in an electrochemical process. The electrodeposition of monomers NaphDOT-R (1 -7) was also performed in dichloromethane (CH2Cl2) and in dichloromethane saturated with water (CH2Cl2 + H2O), to follow an influence of water on micelle formation and its effect on the formed surface nanostructures. Figure 2. NaphDOT-R monomers (1 -7) studied in this work.

Experimental Part

General

All chemicals and solvents were purchased from Sigma Aldrich-Merck and were used without further purification. Thin layer chromatography (TLC) was carried out using Merck TLC silica gel 60 UV-254 aluminum sheets. Purification of synthesized compounds by column chromatography was performed using silica gel 40-60 m (40-250 mesh).

Electrochemical deposition of the films on a gold plate electrode

The electrochemical deposition was performed with a Metrohm Autolab potentiostat Model PGSTAT100 using a three-electrode scheme. The gold plate as the working electrode (2 cm 2 ), a carbon rod (d = 2 mm) as the counter electrode and a saturated calomel electrode (SCE) as the reference electrode were used. 0.1 M tetrabutylammonium perchlorate (Bu4NClO4) in dichloromethane (CH2Cl2) was used as an electrolyte solution. The NaphDOT monomers for electrochemical deposition were used in concentrations of ca. 0.01 M. The used solvent used was either anhydrous DCM or DCM saturated with water (CH2Cl2 + H2O). The last one was used for studies of water influence on the surface morphology. In this case, an excess of water was added to commercial dichloromethane, stirred and left to stay for phase separation. Top water layer was separated from DCM by decantation and bottom layer of DCM saturated with H2O was used in experiments similarly to that in dry DCM. The electrodepositions were performed either (i) in potentiodynamic conditions by cyclic voltammetry (with scanning the potentials between -1 V and the monomer oxidation potential Eox; scan rate: 20 mV s -1 ; number of scans: 1, 3 or 5) or (ii) in potentiostatic conditions at constant potential (E = Eox; deposition charge Qs = 12.5, 25, 50, 100, 200 and 400 mC cm -2 ). After that, in each case, the substrates with the deposited solid films were washed three times with dichloromethane and slowly dried, before studies of their surfaces by SEM.

Surface characterization

The morphology of the surfaces was studied using a JEOL JSM-6700F scanning electron microscope. The surface roughness (arithmetic Ra and quadratic Rq) was determined by optical profilometry using a Wyko NT 1100 optical microscope (Bruker) and the "Vision" software. The measurements were performed in the High Mag Phase Shift Interference (PSI) working mode, field of view 0.5 and objective 50. To study the surface wetting properties, the contact angle measurements were performed using a KRÜSS DSA30 goniometer, and the "Drop Shape Analysis System" software were used. The static contact angles for three different liquids, i.e. water, diiodomethane and n-hexadecane (θW, θDI and θHD, respectively) were determined with the sessile method using 2 µL droplets of probe liquids of various surface tensions: γL = 72.8 mN/m (water), 50.8 mN/m (diiodomethane) and 27.6 mN/m (hexadecane).

Micelles characterization

Solutions containing 0.01 M monomer and 0.1 M tetrabutylammonium perchlorate (Bu4NClO4) in CH2Cl2 + H2O were observed by transmission electron microscopy (TEM) using a JEOL JEM-1400 TEM. For imaging, a drop of 0.45 µm-filtered solution was deposited onto a 400 mesh TEM copper grid with a carbon support film and the exceeding liquid was absorbed with a paper filter to avoid excessive salt deposition onto the TEM grids.

Size measurements on TEM and SEM pictures were performed using ImageJ software. Population distributions were calculated with at least 100 subjects. The mean sizes and standard deviations were calculated fitting the distribution with a gaussian model using the least square method.

Synthesis Naphtho[2,3-b]thieno[3,4-e][1,4]dioxine [NaphDOT (10)][43,56]

The mixture of 3,4-dimethoxythiophene (3) (10.0 g, 69.3 mmol, 1.00 eq.), 2,3-naphthalenediol (2) (40.0 g, 0.25 mol, 3.6 eq.) and p-toluenesulfonic acid monohydrate (2.00 g, 10.4 mmol, 0.15 eq.) in toluene (480 mL) was stirred in an oil bath heated at 130 °C for 2 days. The half of the solvent was evaporated on a rotavapor. After cooling, the mixture was filtered to remove the solid and the solid was washed several times with chloroform. The combined organic filtrates were evaporated to dryness and the residue was purified by column chromatography on silica gel with dichloromethane (DCM):petroleum ether, 1:1 v/v as an eluent to afford pure NaphDOT (10) (3.45 g, 20.7%) as a white solid.

1-(Naphtho[2,3-b]thieno[3,4-e][1,4]dioxin-7-yl)ethenone (11)

Under argon, anhydrous aluminum chloride (3.00 g, 22.3 mmol, 1.50 eq) in anhydrous DCM (80 mL) was added to the solution of NaphDOT (3.60 g, 14.9 mmol, 1.00 eq) in anhydrous DCM (300 mL). The mixture was cooled down and acetyl chloride (2.30 g, 29.7 mmol, 2.00 eq.) was added dropwise to the mixture under slow argon flow. The mixture was stirred at room temperature overnight. The mixture was diluted with 1 M HCl (50 mL), organic layer was separated, and aqueous layer was extracted with DCM. Combined organic layers were dried over Na2SO4, filtered off and the solvent was evaporated. The crude product was purified by column chromatography on silica gel eluting with DCM to afford compound 11 (2.68 g, 63.3%) as a dark brown solid.

Methyl 2-(naphtho[2,3-b]thieno[3,4-e][1,4]dioxin-7-yl)acetate (12)

Thallium (III) nitrate (3.50 g, 7.90 mmol, 1.20 eq) was stirred with trimethoxymethane (8.60 g, 81.2 mmol, 12.3 eq) in methanol (10 mL) for 5 min. Montmorillonite K10 (7.40 g) was added, the mixture was stirred for 10 min and the solvent was evaporated. The solution of 2-acetyl-NaphDOT [START_REF] Ma | Spiro-thiophene derivatives as hole-transport materials for perovskite solar cells[END_REF] (1.86 g, 6.6 mol, 1.00 eq) in a methanol:DCM mixture (1:1 v/v, 200 mL). The mixture was stirred at room temperature for 2 days. The solvent was evaporated, and the residual crude product was purified by column chromatography on silica gel with DCM as an eluent to afford ester 12

(1,44 g, 37.2%) as a beige solid. C NMR (50 MHz, CDCl3): δ 169. 59, 140.35, 140.16, 137.98, 137.55, 130.57, 130.40, 126.83, 125.52, 125.46, 112.98, 112.90, 112.67, 101.54, 52.70, 31.04.

2-(Naphtho[2,3-b]thieno[3,4-e][1,4]dioxin-7-yl)acetic acid [NaphDOT-CH2COOH (13)]

A solution of NaOH (237 mg, 1.50 eq) in water (10 mL) was added dropwise to the solution of ester 12 (1.20 g, 3.9 mmol, 1.00 eq) in ethanol (10 mL). The mixture was heated with stirring at 90 °C overnight. After cooling to room temperature, it was acidified with hydrochloric acid until the pH ~ 3.7, with precipitation of acid 13. The solvent was evaporated and the product dried in oven for a day.

General procedure for esterification of acid 6. Synthesis of NaphDOT monomers 1 -7.

Acid 13 (200 mg, 0.671 mmol, 1.00 eq) was mixed with dicyclohexylcarbodiimide (DCC) (138 mg, 1.00 eq) and a catalytic amount of 4-(dimethylamino)pyridine (DMAP) in absolute acetonitrile (20 mL). After stirring for 30 min, 1.0 eq. of the corresponding alcohol was added to this mixture. The mixture was stirred at room temperature for 6 h. Since the reaction was too slow, another 1.0 eq. of DCC and alcohol were added with 20 mL of dichloromethane to improve the solubility. After a night, the solvents were totally evaporated and the crude product was purified by silica gel column (eluent DCM:cyclohexane, 1:1 v/v).

Results and Discussion

Synthesis of monomers

Synthesis of NaphDOT derivatives is shown in Scheme 1. Unsubstituted NaphDOT [START_REF] Kundu | Hydrophobic polythiophene hole-transport layers to address the moisture-induced decomposition problem of perovskite solar cells[END_REF] was synthesized by acid-catalyzed reaction of 3,4-dimethoxythiophene (8) with 2,3dihydroxynaphthalene (9) according to the procedures described by us previously [START_REF] Poverenov | Flat conjugated polymers combining a relatively low HOMO energy level and band gap: polyselenophenes versus polythiophenes[END_REF][START_REF] Darmanin | A One-step electrodeposition of homogeneous and vertically aligned nanotubes with parahydrophobic properties (high water adhesion)[END_REF]. Its Friedel-Crafts acylation with acetyl chloride gave 2-acetyl-NaphDOT [START_REF] Ma | Spiro-thiophene derivatives as hole-transport materials for perovskite solar cells[END_REF]. The reaction proceeds selectively at the thiophene ring as a more reactive site for an electrophilic attack compared to the naphthalene ring (as evidenced by a thiophene signal at 6.83 ppm with an integral of 1H and (2H + 4H) integrals for protons of 2,3-naphthylenedioxy moiety). The next step of transformation of the acetyl group in 11 into the ester group was done by Willgerodt-Kindler reaction of ketone 11 with trimethyl orthoformate and thallium (III) nitrate [START_REF] Mckillop | Thallium in organic synthesis. XXXIII. A one step synthesis of methyl arylacetates from acetophenones using thallium(III) nitrate (TTN)[END_REF][START_REF] Taylor | Thallium in organic synthesis. 44. Oxidative rearrangements via oxythallation with thallium(III) nitrate supported on clay[END_REF][START_REF] Ho-Hoang | Synthesis and characterization of organic conductors derived from (1H-pyrrol-3-yl)acetic acid esters[END_REF][START_REF] Ho-Hoang | Synthesis and polymerization of 2-(3-pyrrolyl)acetic acid derivatives from pyrrole[END_REF][START_REF] Ho-Hoang | Synthesis and electrochemical characterization of functionalized 3-substituted polypyrroles[END_REF]. Following alkaline hydrolysis of ester 12 gave carboxylic acid 13, which was used as starting materials for synthesis of NaphDOT

Electrochemical deposition of films from NaphDOT-R monomers onto the electrode surface.

Electropolymerization is a common technique to obtain conjugated polymers from electron-rich aromatic and heteroaromatic monomer building blocks [START_REF]Electropolymerization: Concepts, Materials and Applications[END_REF][START_REF]Handbook of Electropolymerization[END_REF]. Among them, polythiophenes and polypyrroles are the most studied polymers obtained by electropolymerization, with a wide range in the monomer structural variations. They have been widely studied as electroactive materials in electrically batteries and supercapacitors, in electrochemical sensors, as conductive layers and in other applications in organic electronics. One of the key features of the electrodeposition of conjugated polymers from a solution of the corresponding monomers using cyclic voltammetry (CV) is that during electropolymerization their CVs, in addition to CV response corresponding to the monomers, show the growth of the CV waves of the polymers deposited on the electrode surface during cyclic scans. This new CV wave from the polymer appears at a lower potential compared to the monomer oxidation in accordance with the increase of the HOMO (highest occupied molecular orbital) energy from the monomer to the conjugated polymer.

We have performed electrochemical deposition of insoluble electroactive films from solutions of monomers NaphDOT-R (1 -7) in dichloromethane (CH2Cl2) and dichloromethane saturated with water (CH2Cl2 + H2O) in potentiodynamic (by cyclic voltammetry, scanning between -1 and +2 V vs SCE (saturated calomel electrode) reference electrode for 1 -5 cycles) and in potentiostatic conditions (at a fixed potential of Eox ~ +2.08 V) (Figure 3). In CV experiments, with anodic scan to the potential of ca. + 2 V, the monomer is oxidized to the radical cation, which then undergo coupling to form the dimer (NaphDOT-R)2 (Scheme 2). This process corresponds to the initial step of the commonly accepted mechanism of electropolymerization. However, it is important to note that since in the studied monomers 1 -7 one thiophene site in position 2 is occupied by the -CH2CO2R group, their electropolymerization to polythiophenes is impossible, and thiophene coupling is stopped at the dimer stage, which (due to poor solubility) are deposited on the surface of the working electrode in the form of colored films. There is also probably monomer in the polymer deposits. For the PheDOT series, we previously observed that the solubility of materials drastically decreased from the monomer to the dimer (and the trimer was found to be very insoluble materials) [START_REF] Perepichka | Electronic properties and reactivity of short-chain oligomers of 3,4-phenylenedioxythiophene (PheDOT)[END_REF]. For NaphDOT series, the materials are even less soluble than that of PheDOTs facilitating films electrodeposition. The situation is different for the monomers 6 and 7 with side carbazole and pyrene groups (and partly for the monomer 5 with 2-naphtyl group). These aromatic units have lower oxidation potentials, comparable to that used in CV experiments in Figure 3 and can also undergo oxidation to form radical cations, followed by coupling and thus electropolymerization. N-Substituted carbazole units are electrochemically oxidized in CV experiments at Eox ~ 1.0 -1.3 V vs SCE (in CH2Cl2) [START_REF] Kortekaas | Reversible charge trapping in biscarbazole-diimide redox polymers with complete luminescence quenching enabling nondestructive read-out by resonance Raman spectroscopy[END_REF][START_REF] Contal | Investigation of polycarbazoles thin films prepared by electrochemical oxidation of synthesized carbazole derivatives[END_REF][START_REF] Taylor | Synthesis and monolayer spreading behaviour of surface-active compounds containing electron-and hole-transporting groups. 2. Carbazole derivatives[END_REF][START_REF] Karon | Carbazole electrochemistry: a short review[END_REF][START_REF] Bekkar | Polycarbazole and its derivatives: synthesis and applications. A review of the last 10 years[END_REF]. Pyrene and its derivatives are oxidized in CV experiments at Eox ~ 1.2 -1.4 V vs SCE [START_REF] Bachman | Electrochemical polymerization of pyrene derivatives on functionalized carbon nanotubes for pseudocapacitive electrodes[END_REF][START_REF] Espinoza | How do amides affect the electronic properties of pyrene?[END_REF][START_REF] Zhao | Twisted configuration pyrene derivative: exhibiting pure blue monomer photoluminescence and electrogenerated chemiluminescence emissions in nonaqueous media[END_REF][START_REF] Lai | Electrogenerated chemiluminescence. Photophysical, electrochemical, and electrogenerated chemiluminescent studies of selected nonplanar pyrenophanes[END_REF][START_REF] Chagas | Superhydrophobic properties of electrodeposited fluorinated polypyrenes[END_REF]. With this, on CV cycling, the dimers formed from monomers 6 and 7 can undergo oxidative coupling at carbazole or pyrene sites to form polymeric films. This is clearly seen from the CV of their electrodeposited films in a monomer-free solution: new CV waves corresponding to the formed polymers appear in the region of 0.8 -1.1 V (Figure 4f,g), a typical region for CV response of electrochemically prepared carbazole and pyrene polymers [START_REF] Waltman | Electrically conducting polymers: a review of the electropolymerization reaction, of the effects of chemical structure on polymer film properties, and of applications towards technology[END_REF][START_REF] Kortekaas | Reversible charge trapping in biscarbazole-diimide redox polymers with complete luminescence quenching enabling nondestructive read-out by resonance Raman spectroscopy[END_REF][START_REF] Contal | Investigation of polycarbazoles thin films prepared by electrochemical oxidation of synthesized carbazole derivatives[END_REF][START_REF] Karon | Carbazole electrochemistry: a short review[END_REF][START_REF] Bekkar | Polycarbazole and its derivatives: synthesis and applications. A review of the last 10 years[END_REF][START_REF] Bachman | Electrochemical polymerization of pyrene derivatives on functionalized carbon nanotubes for pseudocapacitive electrodes[END_REF]. Naphthalene itself is oxidized at ca. 0.4 V higher than pyrene (in CH2Cl2, Eox onset ~ +1.2 V and 0.8 V vs Fc/Fc + , respectively, corresponding to Eox onset ~ +1.6 V and 1.2 V vs SCE, respectively) [START_REF] Bachman | Electrochemical polymerization of pyrene derivatives on functionalized carbon nanotubes for pseudocapacitive electrodes[END_REF], which is also in the range of used potentials of CV electrodeposition in Figure 3. Thus, oxidative coupling and electropolymerization of the monomer NaphDOT-Naph (5) is also possible although less efficient. This is manifested by an appearance of new CV band at lower potentials for the films electrodeposited from this monomer (Figure 4e).

In the second set of experiments, we performed electrodeposition of films from solutions of NaphDOT monomers 1 -7 in dichloromethane saturated with water (CH2Cl2 + H2O). The aim of these experiments is as follows. During electropolymerization, when traces of water are present in the system (from a solvent, electrolyte or from air), formation of O2 and H2 gases is possible within the used range of scanned potentials (eq. 1 and 2). In anodic scans at positive potentials of ~1.5 -2.0 V vs. SCE, an oxidation of water leads to formation of O2 bubbles (eq. 2). However, this redox process is hidden by an oxidation of NaphDOT monomers in the same region. In cathodic scans at negative potentials of ca. -0.2 to -0.8 V, water is reduced to form H2 gas (eq. 1) which is clearly seen on voltammograms (Figure 3; see also Figure S22 in the SI for CV response of CH2Cl2 and (CH2Cl2 + H2O)). Additionally, H2 gas can be formed during CV cycling from the reduction of H + , eq. 4 (protons are generated during water oxidation, eq. 2, and from the polymerization process, eq.

3).

2H2O + 2e -→ H2 (bubbles) + 2OH -

2H2O -4e -→ O2 (bubbles)

+ 4H + (2) n•Monomer -2ne -→ Polymer + 2nH + (3) 2H + + 2e -→ H2 (bubbles) (4)
As expected, CV electrodeposition of monomers 1 -7 in (CH2Cl2 + H2O) system showed an increased intensity of the cathodic peaks from the water reduction at ca. -(0.2 -0.8) V compared to CV experiments in CH2Cl2 (Figure 3), and consequently larger amount of gas bubbles should be formed on cycling in this case.

These H2 and O2 gasses are formed as bubbles at the electrode surface and can act as soft templates during the electropolymerization process around which the polymer growth occurs, thus controlling the surface morphology, nanostructure and hydrophobic properties [START_REF] Fradin | Micellar formation by soft template electropolymerization in organic solvents[END_REF][START_REF] Lai | Electrogenerated chemiluminescence. Photophysical, electrochemical, and electrogenerated chemiluminescent studies of selected nonplanar pyrenophanes[END_REF][START_REF] Chagas | Superhydrophobic properties of electrodeposited fluorinated polypyrenes[END_REF][START_REF] Bousrih | A bioinspired strategy for designing well-ordered nanotubular structures by templateless electropolymerization of thieno[3,4-b]thiophene-based monomers[END_REF].

Previous work of Shi and co-workers on electropolymerization of pyrrole in aqueous solutions

demonstrated the formation of large vertically aligned hollow tubules (∼50-200 μm in diameter)

with opened tops, who explained the observed results as the formation of gas bubbles stabilized by surfactant on the surface of the polypyrrole film and growing the polymer films around these bubbles [START_REF] Qu | Electrochemical growth of polypyrrole microcontainers[END_REF][START_REF] Fakhry | Mechanism of formation of templateless electrogenerated polypyrrole nanostructures[END_REF][START_REF] Debiemme-Chouvy | Electrosynthesis of polypyrrole nano/micro structures using an electrogenerated oriented polypyrrole nanowire array as framework[END_REF]. With electropolymerization in organic solvents, it has been shown with various thiophene derivatives that an increased amount of water influences on the electropolymerized surface nanostructures, allowing to growth the well-ordered nanotubular and nanoporous structures [START_REF] Bousrih | A bioinspired strategy for designing well-ordered nanotubular structures by templateless electropolymerization of thieno[3,4-b]thiophene-based monomers[END_REF][START_REF] Sane | Nanotubular structures through templateless electropolymerization using thieno[3,4-b]thiophene derivatives with different substituents and water content[END_REF][START_REF] Thiam | Designing nanoporous membranes through templateless electropolymerization of thieno[3,4-b]thiophene Derivatives with high water content[END_REF]. We recently demonstrated that reverse micelles stabilized by the monomer and electrolytes in the organic solvent are responsible for the formation of nanoporous structures by electropolymerization [START_REF] Fradin | Micellar formation by soft template electropolymerization in organic solvents[END_REF]. These reverse micelles can act directly as a soft-template for the electropolymerization of NaphDOT monomers. Gas bubbles are formed afterwards from the reverse micelles and released in the solution. In the next sections, we will show and discuss how the formation of reverse micelles affects the surface nanostructure of the resulting films of the dimers and polymers.

Surface morphology and nanostructures

The electrodeposited surfaces have been studied by a scanning electron microscope (SEM). In the case of fluorinated NaphDOT derivatives 1 -3 and NaphDOT-Bn, in which case (as discussed in the previous section) the electrodeposition leads to formation of the dimers (NaphDOT-R)2, the surface is rather smooth for electrodeposition in either in CH2Cl2 or (CH2Cl2 +H2O), with the surface wrinkles observed in some cases (Figure 5). The influence of water content in the solvent results in an increased number of "craters-like" structures, particularly in the case of NaphDOT-C4F9 [START_REF]Handbook of Thiophene-Based Materials: Applications in Organic Electronics and Photonics[END_REF] and NaphDOT-C6F13 (2) in (CH2Cl2 +H2O). Similar effects of water addition have been demonstrated recently by us for some other thiophene derivatives [START_REF] Bousrih | A bioinspired strategy for designing well-ordered nanotubular structures by templateless electropolymerization of thieno[3,4-b]thiophene-based monomers[END_REF][START_REF] Sane | Nanotubular structures through templateless electropolymerization using thieno[3,4-b]thiophene derivatives with different substituents and water content[END_REF][START_REF] Thiam | Designing nanoporous membranes through templateless electropolymerization of thieno[3,4-b]thiophene Derivatives with high water content[END_REF][START_REF] Feng | Petal effect: A superhydrophobic state with high adhesive force[END_REF]. In water saturated solvents, the number of reverse micelles indeed increases but not their size. It is surprising that NaphDOT-Cz [START_REF] Nielsen | Recent advances in transistor performance of polythiophenes[END_REF], which (as discussed above) electropolymerizes at its carbazole sites during CV deposition, also forms rather flat surface structure, and only little water effect is observed. This contrasts with the electropolymerization of thieno [3,4-b]thiophene derivatives functionalized with side carbazole groups, in which case a change of the solvent from CH2Cl2 to (CH2Cl2 + H2O) significantly changes the surface morphology (although in this case, the process is likely occurs mostly as thiophene polymerization) [START_REF] Feng | Petal effect: A superhydrophobic state with high adhesive force[END_REF]. Unique results were especially obtained for the monomers with large aromatic substituents, NaphDOT-Naph [START_REF] Baeg | Toward printed integrated circuits based on unipolar or ambipolar polymer semiconductors[END_REF] and NaphDOT-Pyr [START_REF] Larik | Thiophene-based molecular and polymeric semiconductors for organic field effect transistors and organic thin film transistors[END_REF]. The growth of vertical tiny individual nanotubes (ca. 0.5 -0.7 μm in diameter) was observed by electropolymerizing NaphDOT-Naph in CH2Cl2 (Figure 6). In (CH2Cl2 + H2O) system, their number increased sharply, so that they almost completely occupied the surface and touched the walls between adjacent nanotubes, while the average size of nanotubes decreased to a diameter of ca. 0.1 -0.3 μm (Figure 6). This results in the formation of tight unidirectional vertical nanotubes leading to a nanoporous structure of the surface.

This observation agrees with an increased formation of reverse micelles adsorbed on the surface during electropolymerization, around which growing the polymer occurs. The most interesting features were observed for NaphDOT-Pyr [START_REF] Larik | Thiophene-based molecular and polymeric semiconductors for organic field effect transistors and organic thin film transistors[END_REF]. In CH2Cl2, CV electropolymerization started with a formation of three-dimensional (3D) densely packed tree-like structures (Figure 7, 1 st scan). A similar type of tree-like surface growth was observed for some other thiophenes functionalized with side pyrene groups[Erreur ! Signet non défini.]. Although some tubular structures were also formed on further CV cycling, an intense growth of tree-like structures on the top of the surface, including tubules, was observed (Figure 7, 5 scans). In CH2Cl2 + H2O, the surface morphology was significantly changed: the polymer was growing as long vertically aligned nanotubules (while they are not ideally vertical and in the initial CV scan, some opened tubules collapse to form ribbon structures). After five CV scans, the surface was almost uniformly covered with densely packed long nanotubules (~3 -5 μm long and ~0.4 -0.6 μm in diameter), closed on the top (Figure 7). Therefore, we studied the growth of the surface nanostructure with NaphDOT-Pyr in potentiostatic conditions (Eox = 2.08 V) at different deposition charges, QS, from 12.5 to 400 mC cm -2 (Figure 8). In CH2Cl2, at low deposition charges of 12.5 -50 mC cm -2 , the surface morphology consisted of a high density of spherical nanoparticles (d ~ 30 -100 nm) over the surface, but the morphology is non-porous. Superhydrophobic surfaces formed from spherical nanoparticles have been recently obtained from electropolymerization of a series of 1-substituted pyrenes with side-chain fluoroalkyl groups [START_REF] Chagas | Superhydrophobic properties of electrodeposited fluorinated polypyrenes[END_REF][START_REF] Szczepanski | Recent advances in the study and design of parahydrophobic surfaces: From natural examples to synthetic approaches[END_REF]. With an increase of the deposition charge to 100 -400 mC cm -2 , their number increased, the spherical particles grew in 3D dimensions with the formation of micrometers-size cauliflower agglomerates, which increased the surface roughness and porosity. This difference between the surface structure formed under potentiodynamic and potentiostatic conditions in CH2Cl2 becomes understandable if we consider a soft-template mechanism made of gas bubbles. In that case, only O2 gas bubbles can form during electropolymerization under potentiostatic conditions, which does not lead to porous structures or tubes. Similar to potentiodynamic electropolymerization, in potentiostatic experiments, the influence of water is significant. In (CH2Cl2 + H2O) system, the polymer started to grow

Micellar observation

Solutions of NaphDOT-C4F9 (1), NaphDOT-Cz (6) and NaphDOT-Pyr (7) before electropolymerization in (CH2Cl2 + H2O) were observed by TEM to find reverse micelles.

Reverse micelles were observed in NaphDOT-C4F9 (1) solutions (Figure 9). Their size was measured on random TEM images and compared to the porous nanostructures 'ones in order to verify if they could form the soft template, as for the electropolymerization of NaphDOT in chloroform [START_REF] Darmanin | A One-step electrodeposition of homogeneous and vertically aligned nanotubes with parahydrophobic properties (high water adhesion)[END_REF]. As in dichloromethane electrodeposited nanostructures of NaphDOT are more of a paraboloid shape, if the micelles were to form the structures, they would correspond to the osculating sphere of the paraboloid, that means the sphere which is the most tangent to the summit.

The diameters of the micelles are therefore compared to the diameter of the osculating sphere which is the curvature diameter of the pore. The radius of curvature Rc is calculated with the following formula from the parabola equation:

, where Rp is the radius of the pore at the height Zp.

The micelles observed from NaphDOT-C4F9 (1) solutions have a mean diameter Dm that corresponds to the diameter of curvature of the electrodeposited structures (Table 2), meaning that the micelles surely formed a template for the dimer deposition. The diameter 2Rp of the craters-like structures is smaller than the size of the micelles because the dimers deposition was rather smooth, so that the paraboloid did not grow in height. (1). Scheme of the paraboloid shape with lengths.

Micelles were also observed in NaphDOT-Cz (6) solution (Figure 9) even though the electrodeposited films are smooth. Despite of the carbazole moiety polymerization and the softtemplate created by reverse micelles, no nanostructures were formed, meaning that the bad deposition of NaphDOT-Cz (6) oligomers is responsible for the smooth films.

No reverse micelles were detected in NaphDOT-Pyr (7) solutions, which electrodepositions lead to vertical nanotubes in potentiodynamic conditions. Even if the hypothesis that micelles were not detected for any reason such as contrast or size resolution cannot be totally ruled out, the growth of nanotubes can be explained by the molecular structure of the monomer. The rigid and planar pyrene moiety induces strong π-stacking interactions between the polymer chains that favor an organized and unidimensional growth of the structures, that can lead to nanotubes [START_REF] Grenier | Regiosymmetric poly(dialkylphenylenedioxythiophene)s: electron-rich, stackable π-conjugated nanoribbons[END_REF][START_REF] Darmanin | Exceptionally strong effect of small structural variations in functionalized 3,4-phenylenedioxythiophenes on the surface nanostructure and parahydrophobic properties of their electropolymerized films[END_REF]. This hypothesis is supported by the fact that the NaphDOT-Pyr (7) tubes show a closed extremity, whereas structures generally formed by the micellar-template mechanism present opened pores. In that case, the influence of water on the structures obtained by potentiodynamic and potentiostatic electropolymerizations can be assigned to the formation of gas bubbles in CH2Cl2 + H2O playing the role of soft-template. The formation of these bubbles could indeed occur totally independently from reverse micelles and explain the influence of the electrodeposition method on the structures in CH2Cl2.

These results highlight the effect of the monomer substitute in the formation of reverse micelles by tBuNClO4 in (CH2Cl2 + H2O).

Surface wettability

We have studied the wetting properties of the surfaces electrodeposited from the monomers 1 -7

measuring the apparent angle contacts with the droplets of three liquids differing by their surface tension, i.e. water, diiodomethane and hexadecane (Table 2). Depositions from fluorinated monomers 1 -3 gave the surfaces at the border between being hydrophilic, θW < 90 o , and hydrophobic, θW >90 o (water droplet contact angles θW ~ 71 -117 o , Table 2) due to their relatively small roughness (Figure 5, Table 3). The surfaces are also oleophilic as evidence from small contact angles with diiodomethane and hexadecane (θDI ~ 54 -83 o , θHD ~ 22 -62 o ). No substantial changes in their hydrophobic/oleophilic properties were observed depending on the numbers of CV deposition cycles and the used solvent [CH2Cl2 or (CH2Cl2 + H2O)] (Table 2).

Similar hydrophobic characteristics were observed for NaphDOT-Bn (4) and even for NaphDOT-Cz [START_REF] Baeg | Toward printed integrated circuits based on unipolar or ambipolar polymer semiconductors[END_REF], which is (as discussed above), in contrast to monomers 1 -4, capable to electropolymerize during the deposition but presented smooth films. The water contact angles are more or less held due to the hydrophobicity of the aromatic substitutes even with a smooth roughness. However the diiodomethane and hexadecane contact angles fall drastically compared to fluorinated monomers 1 -3. However, NaphDOT-Cz is slightly more oleophobic after 5 scans in CH2Cl2 + H2O due to the presence of surface structures.

In contrast, NaphDOT-Naph [START_REF] Nielsen | Recent advances in transistor performance of polythiophenes[END_REF] and especially NaphDOT-Pyr [START_REF] Larik | Thiophene-based molecular and polymeric semiconductors for organic field effect transistors and organic thin film transistors[END_REF]

Conclusion

We have successfully synthesized and characterized a series of NaphDOT derivatives, namely the esters of 3,4-(2,3-naphtylenedioxy)thiophene-2-acetic acid with different ester groups.

Potentiodynamic electrodeposition of these compounds from a solution by cyclic voltammetry gave the films of different surface morphology. The NaphDOT esters with fluoroalkyl and benzyl groups gave the dimers, which were precipitated to form relatively flat surface structure, whereas the esters with polymerizable condensed aromatic groups (naphthalene, pyrene) undergo further electropolymerization to form richer surface nanostructure. Significant effect of water presence in a solvent used for electropolymerization has been demonstrated and discussed through different mechanism: soft-template made of reverse micelles or gas bubbles. Thus, in dichloromethane, electropolymerization of pyrene-containing ester NaphDOT-Pyr gave 3D nanostructures of agglomerated spherical nanoparticles or tree-like structures, whereas in dichloromethane saturated with water, unidirectional (1D) vertically oriented nanotubes (~ 0.4 -0.6 μm in diameter and 3 -5 μm in length) were formed. The studies of the wettability of the surfaces using three probe liquids (water, diiodomethane and hexadecane) showed that they are slightly hydrophobic and oleophilic, with some variation of the properties depending on the monomer structures, used solvent and deposition conditions. These data expand our knowledge on the surface nanostructures formation by electropolymerization of electron-rich aromatic compounds making step forward toward controlled surface modification for various applications.

Figure 1 .

 1 Figure 1. Structures of EDOT, PheDOT, substituted R-PheDOT and NaphDOT.

1 H and 13 C

 13 NMR spectra were recorded on a AVANCE I 200MHz -BRUKER with a 60-position sample changer and a QNP -5 mm-gradZ probe spectrometer in CDCl3 or DMSO-d6, operating at 200 MHz ( 1 H) / 50 MHz ( 13 C).

1 H

 1 NMR (200 MHz, CDCl3): δ 7.67 (2H, m, naphthalene), 7.36 (4H, m, naphthalene), 6.52 (2H, s, thiophene).

13 C

 13 NMR (50 MHz, CDCl3): δ 140.65, 138.76, 130.50, 126.82, 125.35, 112.60, 101.08.

1 H

 1 NMR (200 MHz, CDCl3): δ 7.70 -7.64 (2H, m, naphthalene), 7.38 -7.31 (4H, m, naphthalene), 6.44 (1H, s, thiophene), 3.80 (2H, s, CH2), 3.77 (3H, s, CH3).

13

 13

3, 3 , 4 , 4 , 5 , 5 , 6 , 6 , 6 -

 34455666 Nonafluorohexyl 2-(naphtho[2,3-b]thieno[3,4-e][1,4]dioxin-7-yl)acetate [NaphDOT-C4F9 (1)] light beige solid, yield 58.4 mg (17.4%).

3, 3

 3 ,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl-2-(naphtho[2,3-b]thieno[3,4-e][1,4]dioxin-7yl)acetate [NaphDOT-C6F13 (3)] light beige solid, yield 76.4 mg (17.7%).

  10,10,10-Heptadecafluorodecyl-2-(naphtho[2,3-b]thieno[3,4e][1,4]dioxin-7-yl)acetate [NaphDOT-C8F17 (3)] light beige solid, yield 63.4 mg (12.7%).

monomers 1 -Scheme 1 .

 11 Scheme 1. Synthesis of NaphDOT monomers 1 -7.

Scheme 2 .

 2 Scheme 2. Electrochemical dimerization of NaphDOT-R. Red dashed line shows attractive S•••O contacts which planarize the dimers (NaphDOT-R)2.

Figure 3 .

 3 Figure 3. Electrodeposition of NaphDOT monomers 1 -7 in CH2Cl2 (a,c,e,g,i,k,m) and in dichloromethane saturated with water, (CH2Cl2 +H2O) (b,d,f,h,j,l,n) by cyclic voltammetry; electrolyte: 0.1 M Bu4NclO4; scan rate 20 mV s -1 ; first 5 scans have been shown.

Figure 4 . 1 - 7 .

 417 Figure 4. Cyclic voltammograms of electrodeposed films on gold plate electrode from NaphDOT monomers 1 -7. Monomer-free 0.1 M Bu4NClO4 / CH2Cl2; scan rate 20 mV s -1 .

Figure 5 .

 5 Figure 5. SEM images of the surface electrodepositions from NaphDOT-C4H9, NaphDOT-C6H13, NaphDOT-C8H17, NaphDOT-C4H9, NaphDOT-Bn and NaphDOT-Cz (1 -5) in CH2Cl2 and in (CH2Cl2 + H2O) with 0.1 M Bu4NClO4 as an electrolyte. Potentiodynamic deposition for 3 CV cycles between -1 V and Eox. Magnification: ×10,000.

Figure 6 .

 6 Figure 6. SEM images of electrodeposited surfaces from NaphDOT-Naph (5) in either CH2Cl2 or (CH2Cl2 + H2O) with 0.1 M Bu4NClO4. Potentiodynamic electrodeposition for 1, 3 and 5 CV scans between -1 V and Eox. Right two columns are SEM images with a substrate inclination of 45 o . Magnification: ×10,000 (left) and X25,000 (right).

Figure 7 .

 7 Figure 7. SEM images of electrodeposited surfaces from NaphDOT-Pyr in either CH2Cl2 or (CH2Cl2 + H2O) with 0.1 M Bu4NClO4. Potentiodynamic electrodeposition for 1, 3 and 5 CV scans between -1 V and Eox. Right two columns are SEM images with a substrate inclination of 45 o . Magnification: ×10,000

  unidirectionally (1D) in the form of open-top nanotubes (QS ~ 12.5 -50 mC cm -2 ). With an increase of the deposition charge (QS ~ 100 -400 mC cm -2 ), the tops of nanotubes closed, and their height constantly increased, reaching a length of ~1.5 -2.5 μm, while their diameter remained virtually unchanged at a level of ~0.25 -0.45 μm. The water influence on the nanostructures was further investigated by studying the micellar template for several NaphDOT derivatives.

Figure 8 .

 8 Figure 8. SEM images of electrodeposited surfaces from NaphDOT-Pyr polymer in both CH2Cl2 (right column) and CH2Cl2 + H2O (left and middle columns) with 0.1 M Bu4NClO4 at constant potential of Eox = 2.08 V for different depositions charges of Qs = 12.5, 25, 50, 100, 200 and 400

Figure 9 .

 9 Figure 9. TEM images of NaphDOT-C4F9 (1) and NaphDOT-Cz (6) in (CH2Cl2 + H2O) containing Bu4NClO4 as electrolytes. Gaussian distributions of the measured diameters of the micelles (Dm) and the pores (2Rp) and the calculated curvature diameter (2Rc) for NaphDOT-C4F9

  NMR (50 MHz, CDCl3): δ 189.11, 140.72, 139.56, 139.43, 138.55, 130.93, 130.37, 126.98, 126.91, 126.00, 125.77, 120.94, 113.21, 112.83, 108.45, 29.31.

	1 H NMR (200 MHz, CDCl3): δ 7.73 -7.68 (2H, m, naphthalene), 7.46 -7.35 (4H, m, naphthalene),
	6.83 (1H, s, thiophene), 2.69 (3H, s, CH3).

13

C

  CDCl3): δ 169.38, 140.43, 140.37, 138.13, 136.35, 130.49, 130.42, 126.80, 126.78, 125.38, 125.35, 112.67, 112.58, 109.19, 99.42, 57.14 (m, from C4F9), 31.02, 30.40 (m, from

	1 H NMR (200 MHz, CDCl3): δ 7.69 -7.64 (2H, m, naphthalene), 7.38 -7.31 (4H, m, naphthalene),
	6.45 (1H, s, thiophene), 4.48 (2H, t, J = 6.6 Hz, CH2CO2CH2CH2R), 3.81 (2H, s,
	CH2CO2CH2CH2R), 2.53 (2H, tt, J = 18.2, 6.6 Hz, CH2CO2CH2CH2R).
	C4F9).

13

C NMR

(50 MHz,

(naphtho[2,3-b]thieno[3,4-e][1,4]dioxin-7-yl)acetate [NaphDOT-Bn (4)]

  H NMR (200 MHz, CDCl3): δ 7.68 -7.64 (2H, m, naphthalene), 7.38 -7.31 (4H, m, naphthalene), 6.45 (1H, s, thiophene), 4.47 (2H, tt, J = 6.6 Hz, CH2CO2CH2CH2R), 3.81 (2H, s, CH2CO2CH2CH2R), 2.53 (2H, tt, J = 18.2, 6.4 Hz, CH2CO2CH2CH2R). NMR (50 MHz, CDCl3): δ 169.39, 140.43, 140.38, 138.14, 136.36, 130.50, 130.43, 126.79, NMR (50 MHz, CDCl3): δ 169.59, 140.47, 140.41, 138.08, 135.52, 130.45, 130.40, 128.57, 128.35, 128.29, 126.78, 125.30, 112.68, 112.52, 109.76, 99.31, 67.10, 31.30.

	126.78, 125.38, 125.34, 112.67, 112.59, 109.20, 99.42, 57.18 (m, from C8F17), 31.04, 29.70 (m,
	from C8F17).
	Benzyl 2-beige solid, yield 77.1 mg (29.6%).
	1 H NMR (200 MHz, CDCl3): δ 7.69 -7.64 (2H, m, naphthalene), 7.40 -7.31 (9H, m, naphthalene
	+ Ph), 6.44 (1H, s, thiophene), 5.21 (2H, s, CH2CO2CH2R), 3.84 (2H, s, CH2CO2CH2R).
	Naphtalen-2

1 13 C 13 C

-ylmethyl 2-(naphtho[2,3-b]thieno[3,4-e][1,4]dioxin-7-yl)acetate [NaphDOT-Naph (5)]

	beige solid, yield 76.4 mg (26.0%).
	1 H NMR (200 MHz, CDCl3): δ 7.84 -7.76 (4H, m, 2-naphtyl), 7.67 -7.56 (2H, m, naphthalene),
	7.48 -7.43 (3H, m, 2-naphtyl + naphthalene), 7.32 (3H, m, 2-naphtyl + naphthalene), 7.29 (1H, s,
	2-naphphtyl), 6.43 (1H, s, thiophene), 5.35 (2H, s, CH2CO2CH2R), 3.84 (2H, s, CH2CO2CH2R).
	13 C NMR (50 MHz, CDCl3): δ 169.61, 140.46, 140.39, 138.11, 133.13, 132.92, 130.45, 130.39,
	128.39, 127.98, 127.68, 127.46, 126.78, 126.31, 125.85, 125.31, 125.27, 112.69, 112.52, 109.75,
	99.30, 67.22, 31.39.

2-(Carbazol-9-yl)ethyl 2-(naphtho[2,3-b]thieno[3,4-e][1,4]dioxin-7-yl)acetate [NaphDOT-Cz (6)]

	Pyren-1
	beige solid, yield 76.5 mg (23.2%).
	1 H NMR (200 MHz, CDCl3): δ 8.07 -8.01 (2H, m), 7.70 -7.61 (2H, m), 7.47 -7.31 (8H, m), 7.24
	-7.17 (2H, m), 6.40 (1H, s, thiophene), 4.60 (4H, m, CH2CO2CH2CH2R), 3.63 (2H, s,
	CH2CO2CH2CH2R).
	13 C NMR (50 MHz, CDCl3): δ 166.95, 140.41, 140.37, 138.02, 136.29, 130.41, 130.36, 126.81,
	126.78, 125.84, 125.33, 125.30, 124.60, 123.04, 120.40, 119.28, 112.51, 108.40, 99.31, 31.09,
	29.69, 24.83.

-ylmethyl 2-(naphtho[2,3-b]thieno[3,4-e][1,4]dioxin-7-yl)acetate [NaphDOT-Pyr (7)] dark

  orange solid, yield 115.9 mg (33.7%). H NMR (200 MHz, CDCl3): δ 7.95-8.26 (9H, m), 7.52-7.58 (2H, m), 7.28-7.39 (4H, m), 6.89 (1H, s, thiophene), 5.91 (2H, s, CH2CO2CH2R), 3.81 (2H, s, CH2CO2CH2R). CDCl3): δ 169.67, 140.11, 138.12, 131.80, 131.02, 130.24, 130.15, 128.39, 128.17, 127.96, 127.80, 127.14, 126.72, 126.69, 125.93, 125.49, 125.37, 125.13, 125.07, 124.43, 122.83, 112.34, 112.19, 109.60, 99.03, 65.73, 31.63, 26.90.

	13 C NMR (50 MHz,

1

Table 1 .

 1 Gaussian fitting data of the measured and calculated distributions.

	Monomer	Zp (nm)	2Rp (nm) µ ± σ	2Rc (nm) µ ± σ	Dm (nm) µ ± σ
	NaphDOT-C4F9	35 ± 10	130 ± 45	501 ± 243	444 ± 108

Table 2 .

 2 are more hydrophobic thanks to nanotubes and rough nanostructures. A high amount of air is trapped between the water droplet and the rough surfaces leading to an increase of the surface hydrophobicity even if these polymers are intrinsically hydrophilic. All surfaces are para-hydrophobic, meaning the adhesion of the droplet is very strong even if the substrate is inclined, a behavior that is coherent with intermediate states between the Wenzel and Cassie-Baxter states[88,89]. Wettability data: apparent contact angles of the three probe liquids [water (θW), 600 diiodomethane (θDI) and hexadecane (θHD)] as a function of the solvent used for electrodeposition 601 [CH2Cl2 or (CH2Cl2 + H2O)] and the number of deposition cycles by cyclic voltammetry. 602 Monomers used for electrodeposition. b Deposition conditions: 0.1 M Bu4NClO4; scan rate 20 mV s -1 . c θW, 603 θDI, and θHD are apparent contact angles of the water, diiodomethane and hexadecane droplets, respectively,

		Monomer a	Solvent for deposition b	Number of deposition scans	Water c θW [deg]	Diiodomethane c θDI [deg]	Hexadecane c θHD [deg]
		NaphDOT-C4F9 (1)	CH2Cl2	1	71 ± 4	68 ± 4	36 ± 4
				3	71 ± 3	60 ± 2	33 ± 4
				5	76 ± 7	54 ± 3	28 ± 4
			CH2Cl2 + H2O	1	83 ± 8	64 ± 5	35 ± 6
				3	74 ± 8	56 ± 7	22 ± 5
				5	102 ± 1	65 ± 3	28 ± 4
		NaphDOT-C6F13 (2)	CH2Cl2	1	93 ± 3	60 ± 2	35 ± 1
				3	92 ± 5	71 ± 4	53 ± 3
				5	117 ± 2	74 ± 2	54 ± 3
			CH2Cl2 + H2O	1	62 ± 7	62 ± 3	35 ± 5
				3	72 ± 4	83 ± 3	50 ± 12
				5	78 ± 3	76 ± 2	58 ± 7
		NaphDOT-C8F17 (3)	CH2Cl2	1	104 ± 3	78 ± 5	62 ± 3
				3	93 ± 4	73 ± 2	51 ± 4
				5	81 ± 6	71 ± 3	48 ± 3
			CH2Cl2 + H2O	1	85 ± 2	70 ± 3	38 ± 4
				3	80 ± 6	67 ± 4	37 ± 4
				5	77 ± 6	73 ± 2	54 ± 10
		NaphDOT-Bn (4)	CH2Cl2	1	68 ± 7	37 ± 4	0
				3	58 ± 17	36 ± 5	0
				5	66 ± 2	44 ± 5	0
			CH2Cl2 + H2O	1	84 ± 5	54 ± 6	0
				3	63 ± 2	24 ± 3	0
				5	67 ± 2	28 ± 4	0
		NaphDOT-Naph (5)	CH2Cl2	1	89 ± 1	37 ± 2	0
				3	92 ± 10	30 ± 4	0
				5	97 ± 9	35 ± 6	0
			CH2Cl2 + H2O	1	106 ± 5	26 ± 9	0
				3	69 ± 5	35 ± 11	0
				5	97 ± 5	34 ± 6	0
		NaphDOT-Cz (6)	CH2Cl2	1	76 ± 7	42 ± 1	0
				3	85 ± 9	43 ± 6	0
				5	78 ± 2	48 ± 6	0
			CH2Cl2 + H2O	1	99 ± 5	17 ± 5	0
				3	88 ± 4	49 ± 5	0
				5	90 ± 8	65 ± 3	25 ± 6
		NaphDOT-Pyr (7)	CH2Cl2	1	128 ± 9	0	0
				3	-	0	0
				5	-	0	0
			CH2Cl2 + H2O	1	68 ± 13	0	0
				3	77 ± 7	0	0
				5	110 ± 26	0	0
	a 604
	605	with the electrodeposited films surface.
	606

Table 3 .

 3 Roughness parameters for electrodeposited films on Au plate electrode. a Electrodeposition was performed by CV in potentiodynamic conditions with 0.1 M Bu4NClO4 as an electrolyte; scan rate 20 mV s -1 . b Monomers used for electrodeposition. c Ra is mean arithmetic roughness and Rq is mean quadratic roughness of the surface.

	Monomer b	Number of deposition scans	CH2Cl2 Ra (nm) c Rq (nm) c	CH2Cl2 + H2O Ra (nm) c Rq (nm) c
	NaphDOT-C4F9 (1)	3	173 ± 63	253 ± 77	44 ± 19	62 ± 22
	NaphDOT-C6F13 (2)	3	215 ± 46	305 ± 62	102 ± 41	133 ± 54
	NaphDOT-C8F17 (3)	3	109 ± 44	145 ± 55	59 ± 13	102 ± 10
	NaphDOT-Bn (4)	3	391 ± 44	499 ± 52	317 ± 114	416 ± 134
		1	33 ± 24	29 ± 26	31 ± 8	48 ± 9
	NaphDOT-Naph (5)	3	141 ± 90	199 ± 117	113 ± 39	161 ± 56
		5	210 ± 70	281 ± 87	186 ± 34	239 ± 64
	NaphDOT-Cz (6)	1	273 ± 122	374 ± 157	38 ± 13	58 ± 17
		1	-	-	-	-
	NaphDOT-Pyr (7)	3	-	-	-	-
		5	-	-	-	-

a

ACKNOWLEDGEMENTS

The authors would like to acknowledge Agence Innovation Défense for their grant and support. This work has been supported by CNRS GDR 2088 « BIOMIM ».

Declaration of Competing Interest

There are no conflicts of interest to declare.

Supporting Information

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