New Layered Polythiophene-Silica Composite Through the Self-Assembly and Polymerization of Thiophene-Based Silylated Molecular Precursors

A new layered hybrid polythiophene-silica material was obtained directly by hydrolysis and polycondensation (sol-gel) of a silylated-thiophene bifunctional precursor, and its subsequent oxidative polymerization by FeCl3. This precursor was judiciously designed to guarantee its self-assembly and the formation of a lamellar polymer-silica structure, exploiting the cooperative effect between the hydrogen bonding interactions, originating from the ureido groups and the π-stacking interactions between the thiophene units. The lamellar structure of the polythiophene-silica composite was confirmed by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) analyses. The solid-state nuclear magnetic resonance (NMR), UV-Vis, and photoluminescence spectra unambiguously indicate the incorporation of polythiophene into the silica matrix. Our work demonstrates that using a polymerizable silylated-thiophene precursor is an efficient approach towards the formation of nanostructured conjugated polymer-based hybrid materials.


Introduction
Conjugated polymers (CPs) have demonstrated a great potential as an active component in a wide range of electronic and optoelectronic devices, such as polymer solar cells [1][2][3], organic field-effect transistors [4][5][6], polymer light emitting diodes [7,8], organic batteries [9,10], and biosensors [11,12]. Such devices generally involve complex multi-layered architectures, where the synergistic combination of the CPs and the built-in components determine the intrinsic performance of the devices [13,14]. Indeed, the performances of the devices are intimately related to the interfacial contact between the active layers and the nanoscale morphology of the polymer (which is intrinsically linked to the optoelectronic properties of the polymer) [15][16][17]. In this respect, controlling the inter-chain interactions, the orientation, and the conformation of the polymer chains are required to minimize the undesirable charge transfer, increase the charge carrier mobilities, and thus, develop devices with enhanced optical and electronic properties [18][19][20]. CPs are also known to be sensitive to photoinduced oxidation, which affects their electronic and photoconductive properties [21,22].
Incorporation of CPs into an inorganic matrix represents an elegant approach to indirectly control the alignment of polymer chains, to reduce interchain effects by separating the chains and to improve the environmental stability of polymers [23][24][25]. Consequently, enhanced photoluminescence properties have been achieved through the confinement of polymer chains into nanoporous inorganic 3-(8′-Azidooctyl)thiophene (2) was first prepared from 3-(8′-bromooctyl)thiophene (1), by a nucleophilic aliphatic substitution. The presence of the azido group was evidenced by the azide antisymmetric stretching band at 2092 cm −1 in the IR spectrum of 2 ( Figure S1 in the Supplementary Materials). The substitution of bromide by azide was also confirmed by 1 H and 13 C{ 1 H} NMR spectroscopies, with the signals at 3.25 ppm and 51.9 ppm, respectively, corresponding to CH2N3 (respectively, Figures S2 and S3 in the Supplementary Materials). In the second step, this compound was reduced into the corresponding amine 3 with LiAlH4 in THF. The IR spectrum of 3 clearly indicates the presence of the asymmetrical and symmetrical N-H stretching vibrations at 3400 and 3300 cm −1 , characteristic of the primary amine function ( Figure S4 in the Supplementary Materials). ESI-TOF mass spectrometry (positive mode) also revealed the expected m/z = 212.1 Da [M + H + ]. Finally, the reaction between the primary amine 3 and 3-(isocyanatopropyl)triethoxysilane quantitatively afforded the precursor 4. Formation of 4 was confirmed by 1 H, 13 C{ 1 H}, and 29 Si{ 1 H} NMR spectroscopies in CDCl3 (respectively, Figures S7-S9 in the Supplementary Materials). The presence of the trialkoxysilyl group was attested in the 1 H-NMR spectrum of 4 by the triplet and quadruplet, at 3.78 and 1.19 ppm, respectively, which were assigned to the OCH2 and CH3 groups ( Figure S7 in the Supplementary Materials). As expected, the 29 Si{ 1 H} spectrum of 4 exhibits only one signal at −45.2 ppm, corresponding to RSi(OEt)3 moieties ( Figure S9 in the Supplementary Materials).

Synthesis of the Lamellar Thiophene-Silica Hybrid Material
The hydrolysis and condensation of the monosilylated precursor 4 in suspension in water at pH = 1.5 were first performed at room temperature for 48 h (Scheme 2). In fact, at this pH, the hydrolysis takes place while the polycondensation is induced by the self-assembly of the precursor to give the hybrid material M4 [52].
After this time, the obtained precipitate was filtered, treated by following the usual work-up and dried (see Experimental Section). The IR spectrum of the resulting solid M425 revealed the presence of a very broad band at 3200 cm −1 , corresponding to the residual O-H bonds and indicating an incomplete polycondensation reaction ( Figure S10 in the Supplementary Materials). To improve the polycondensation rate, the hybrid material M425 obtained previously was suspended in acidic water (pH = 1.5) at 110 °C for 24 h. Treatment of M425 in these conditions quantitatively afforded M4110 as a white powder. The 29 Si CPMAS NMR spectrum of M4110 showed a high rate of T 3 species (major peak around −66.0 ppm) ( Figure 1). The higher degree of polycondensation for M4110 was also confirmed from the results of the elemental analyses since values of C, H, N, and S content closer to theoretical ones were found. 3-(8 -Azidooctyl)thiophene (2) was first prepared from 3-(8 -bromooctyl)thiophene (1), by a nucleophilic aliphatic substitution. The presence of the azido group was evidenced by the azide antisymmetric stretching band at 2092 cm −1 in the IR spectrum of 2 ( Figure S1 in the Supplementary Materials). The substitution of bromide by azide was also confirmed by 1 H and 13 C{ 1 H} NMR spectroscopies, with the signals at 3.25 ppm and 51.9 ppm, respectively, corresponding to CH 2 N 3 (respectively, Figures S2 and S3 in the Supplementary Materials). In the second step, this compound was reduced into the corresponding amine 3 with LiAlH 4 in THF. The IR spectrum of 3 clearly indicates the presence of the asymmetrical and symmetrical N-H stretching vibrations at 3400 and 3300 cm −1 , characteristic of the primary amine function ( Figure S4 in the Supplementary Materials). ESI-TOF mass spectrometry (positive mode) also revealed the expected m/z = 212.1 Da [M + H + ]. Finally, the reaction between the primary amine 3 and 3-(isocyanatopropyl)triethoxysilane quantitatively afforded the precursor 4. Formation of 4 was confirmed by 1 H, 13 C{ 1 H}, and 29 Si{ 1 H} NMR spectroscopies in CDCl 3 (respectively, Figures S7-S9 in the Supplementary Materials). The presence of the trialkoxysilyl group was attested in the 1 H-NMR spectrum of 4 by the triplet and quadruplet, at 3.78 and 1.19 ppm, respectively, which were assigned to the OCH 2 and CH 3 groups ( Figure S7 in the Supplementary Materials). As expected, the 29 Si{ 1 H} spectrum of 4 exhibits only one signal at −45.2 ppm, corresponding to RSi(OEt) 3 moieties ( Figure S9 in the Supplementary Materials).

Synthesis of the Lamellar Thiophene-Silica Hybrid Material
The hydrolysis and condensation of the monosilylated precursor 4 in suspension in water at pH = 1.5 were first performed at room temperature for 48 h (Scheme 2). In fact, at this pH, the hydrolysis takes place while the polycondensation is induced by the self-assembly of the precursor to give the hybrid material M4 [52].
After this time, the obtained precipitate was filtered, treated by following the usual work-up and dried (see Experimental Section). The IR spectrum of the resulting solid M4 25 revealed the presence of a very broad band at 3200 cm −1 , corresponding to the residual O-H bonds and indicating an incomplete polycondensation reaction ( Figure S10 in the Supplementary Materials). To improve the polycondensation rate, the hybrid material M4 25 obtained previously was suspended in acidic water (pH = 1.5) at 110 • C for 24 h. Treatment of M4 25 in these conditions quantitatively afforded M4 110 as a white powder. The 29 Si CPMAS NMR spectrum of M4 110 showed a high rate of T 3 species (major peak around −66.0 ppm) ( Figure 1). The higher degree of polycondensation for M4 110 was also confirmed from the results of the elemental analyses since values of C, H, N, and S content closer to theoretical ones were found.    The extent of the intermolecular hydrogen bonding due to the ureido moieties was examined in M4 110 by FT-IR spectroscopy. Here, the differences (∆ν) between the two vibration amide modes (amide I (ν C=O ) and amide II (δ NH )) of the ureido group were used as a probe to evaluate the strength of the hydrogen bonds between the ureido groups: the lower the ∆ν values, the stronger the hydrogen bonding interactions [53][54][55]. From the IR spectrum of M4 110 , a ∆ν of 50 cm −1 was calculated. This difference was of the same magnitude as the ones found for the monosilylated precursors of the formula (EtO) 3 Si(CH 2 ) 3 NH(C=O)NHC n H 2n+1 (n = 8 and 12), and indicated significant hydrogen-bonding interactions (see Experimental section and Figure S8 in the Supplementary Materials) [55]. It was also interesting to note that no band was observed at 1680 cm −1 indicating no free ureido groups in this hybrid material.
The X-ray powder diffraction (XRD) pattern of M4 110 exhibited diffraction peaks, which are characteristic of a lamellar structure ( Figure 2). Indeed, peaks at 2θ~2.86 • and 5.57 • were observed, corresponding to the (100) and (200) orders with an interlayer distance of 3.1 nm (calculated using Bragg's law nλ = 2d × sinθ with λ(CuK α1 ) = 1.542 Å). This value was different from the theoretical distance estimated by the ChemDraw3D calculation (3.5 nm) and corresponding to the two N-propyl-N -(3-octylthiophene)urea units. This difference could be explained by the inclination of the alkylene chains with respect to the plane formed by the condensed siloxane units, which was not taken into account for the ChemDraw 3D calculation [56]. It is worth noting that a broad reflection, centered at 2 θ~21 • was also observed, corresponding to a distance of 4.2 Å, which is a typical value for thiophene interchain distances and also close to what can be found among siloxane units [56,57].
To determine the morphology of the hybrid material M4 110 on a microscopic scale, SEM analyses were performed. SEM images revealed that M4 110 exhibited a lamellar morphology (Figure 3, left). Further evidence for the lamellar structure was given by transmission electron microscopy (TEM) (see Figure 3, right), which displayed defined striped patterns. The thermal fragility of the material, due to a high organic content, explains the low-image resolution. The extent of the intermolecular hydrogen bonding due to the ureido moieties was examined in M4110 by FT-IR spectroscopy. Here, the differences (∆ν) between the two vibration amide modes (amide I (νC=O) and amide II (δNH)) of the ureido group were used as a probe to evaluate the strength of the hydrogen bonds between the ureido groups: the lower the ∆ν values, the stronger the hydrogen bonding interactions [53][54][55]. From the IR spectrum of M4110, a ∆ν of 50 cm −1 was calculated. This difference was of the same magnitude as the ones found for the monosilylated precursors of the formula (EtO)3Si(CH2)3NH(C=O)NHCnH2n+1 (n = 8 and 12), and indicated significant hydrogenbonding interactions (see Experimental section and Figure S8 in the Supplementary Materials) [55]. It was also interesting to note that no band was observed at 1680 cm −1 indicating no free ureido groups in this hybrid material.
The X-ray powder diffraction (XRD) pattern of M4110 exhibited diffraction peaks, which are characteristic of a lamellar structure ( Figure 2). Indeed, peaks at 2θ ~ 2.86° and 5.57° were observed, corresponding to the (100) and (200) orders with an interlayer distance of 3.1 nm (calculated using Bragg's law nλ = 2d × sinθ with λ(CuKα1) = 1.542 Å). This value was different from the theoretical distance estimated by the ChemDraw3D calculation (3.5 nm) and corresponding to the two N-propyl-N′-(3-octylthiophene)urea units. This difference could be explained by the inclination of the alkylene chains with respect to the plane formed by the condensed siloxane units, which was not taken into account for the ChemDraw 3D calculation [56]. It is worth noting that a broad reflection, centered at 2 θ ~ 21° was also observed, corresponding to a distance of 4.2 Å, which is a typical value for thiophene interchain distances and also close to what can be found among siloxane units [56,57]. To determine the morphology of the hybrid material M4110 on a microscopic scale, SEM analyses were performed. SEM images revealed that M4110 exhibited a lamellar morphology (Figure 3, left). Further evidence for the lamellar structure was given by transmission electron microscopy (TEM) (see Figure  3, right), which displayed defined striped patterns. The thermal fragility of the material, due to a high organic content, explains the low-image resolution.  Taken together, all these data indicate that the self-assembly of the hybrid materials operated as expected, through the formation of hydrogen bonding interactions between the ureido groups, van der Waals interactions between the alkylene chains, and π-π stacking interactions between thiophene units [58]. As such, the acid hydrolysis of alkoxysilyl groups into silanol in these "pre-organized" molecular structures allowed obtaining ordered hybrid materials.

The preparation of Lamellar Polythiophene-Silica Hybrid Material
The dense packing of the thiophene groups in the interlamellar space of the hybrid materials allowed their polymerization to form the lamellar polythiophene-silica hybrid material P4 (Scheme 2). In situ thiophene polymerization was carried out by mixing M4110 with anhydrous FeCl3, a wellknown thiophene polymerization oxidant [59], in chloroform, and stirring the mixture, at room temperature, for 72 h. The color of the reaction medium gradually shifted from orange (beginning of the reaction) to dark green, after 72 h ( Figure S11 in the Supplementary Materials), due to the change in oxidation state of iron (III) to iron (II). After three days, the suspension was filtered and the resulting powder was thoroughly washed with water and methanol to eliminate the residual iron salts.
The hybrid material P4 was analyzed by 13 C solid-state NMR, and compared to M4110 ( Figure  S12 in the Supplementary Materials). After polymerization, noticeable changes were observed in the 13 C chemical shifts of both the aromatic and alkyl carbons, showing that their local environment was modified. Moreover, a significant broadening of the 13 C resonances was observed, especially for the CH2 groups, which could be explained by a decrease in "mobility" of the alkyl chains, due to the rigidification of the material. Although the detailed assignment of the 13 C resonances has not been achieved so far (as it would require additional high-resolution solid-state NMR experiments), these observations strongly suggest that some interconnection between the thiophene rings had occurred. Moreover, the XRD pattern of P4 (Figure 1) shows the preservation of the diffraction peaks, after polymerization, indicating that the lamellar structure was not affected by this polymerization process. Two additional peaks at 2θ = 11.84° and 18.20°, corresponding to d-spacings of 7.5 Å and 4.8 Å, respectively were noticed. These peaks might correspond to the higher-order reflection peaks of the obtained polymer [60,61]. The diffraction peak at 2θ ~ 21° might also indicate the persistence of the interactions between the chains in the polymer backbones [62,63]. Thermal stability of P4 was evaluated by the thermal gravimetric analysis (TGA), from 25 °C to 600 °C, in air. The obtained curve ( Figure S13 in the Supplementary Materials) showed that the hybrid material remained stable up to 180 °C and the loss of mass percentage between 180 °C and 600 °C was estimated to be around 75%, which is close to the theoretical percentage (78%). Taken together, all these data indicate that the self-assembly of the hybrid materials operated as expected, through the formation of hydrogen bonding interactions between the ureido groups, van der Waals interactions between the alkylene chains, and π-π stacking interactions between thiophene units [58]. As such, the acid hydrolysis of alkoxysilyl groups into silanol in these "pre-organized" molecular structures allowed obtaining ordered hybrid materials.

The preparation of Lamellar Polythiophene-Silica Hybrid Material
The dense packing of the thiophene groups in the interlamellar space of the hybrid materials allowed their polymerization to form the lamellar polythiophene-silica hybrid material P4 (Scheme 2). In situ thiophene polymerization was carried out by mixing M4 110 with anhydrous FeCl 3 , a well-known thiophene polymerization oxidant [59], in chloroform, and stirring the mixture, at room temperature, for 72 h. The color of the reaction medium gradually shifted from orange (beginning of the reaction) to dark green, after 72 h ( Figure S11 in the Supplementary Materials), due to the change in oxidation state of iron (III) to iron (II). After three days, the suspension was filtered and the resulting powder was thoroughly washed with water and methanol to eliminate the residual iron salts.
The hybrid material P4 was analyzed by 13 C solid-state NMR, and compared to M4 110 (Figure S12 in the Supplementary Materials). After polymerization, noticeable changes were observed in the 13 C chemical shifts of both the aromatic and alkyl carbons, showing that their local environment was modified. Moreover, a significant broadening of the 13 C resonances was observed, especially for the CH 2 groups, which could be explained by a decrease in "mobility" of the alkyl chains, due to the rigidification of the material. Although the detailed assignment of the 13 C resonances has not been achieved so far (as it would require additional high-resolution solid-state NMR experiments), these observations strongly suggest that some interconnection between the thiophene rings had occurred. Moreover, the XRD pattern of P4 (Figure 1) shows the preservation of the diffraction peaks, after polymerization, indicating that the lamellar structure was not affected by this polymerization process. Two additional peaks at 2θ = 11.84 • and 18.20 • , corresponding to d-spacings of 7.5 Å and 4.8 Å, respectively were noticed. These peaks might correspond to the higher-order reflection peaks of the obtained polymer [60,61]. The diffraction peak at 2θ~21 • might also indicate the persistence of the interactions between the chains in the polymer backbones [62,63]. Thermal stability of P4 was evaluated by the thermal gravimetric analysis (TGA), from 25 • C to 600 • C, in air. The obtained curve ( Figure S13 in the Supplementary Materials) showed that the hybrid material remained stable up to 180 • C and the loss of mass percentage between 180 • C and 600 • C was estimated to be around 75%, which is close to the theoretical percentage (78%).
In situ polymerization leads to a change in color from white for M4 110 to a reddish orange for P4, suggesting the formation of conjugated polythiophene chains. UV-vis absorption and fluorescence spectra were recorded to investigate the optical properties of the resulting polythiophene-silica hybrid material P4 (Figure 4). P4 exhibited the maximum absorption and emission wavelengths, at 385 and 582 nm, respectively. Theoretical calculations and experimental measurements have shown that a linear relationship was typically observed between the adiabatic transition energy (E 00 ) and the inverse of the number of thiophene rings, allowing the determination of the effective conjugation length [64,65]. E 00 was determined experimentally, by determining the intersection of the normalized absorption and emission spectra. Thus, by exploiting the relationship between E 00 and the inverse of the number of thiophene units, the effective conjugation length (ECL) could be estimated. An ECL of~2.9 nm, corresponding to seven substituted thiophene rings was found from the intersection of the absorption and emission spectra, at 527 nm. The length of alkyl chains at the third position of the thiophene ring, in the polymerization of the thiophene monomers, has been found to significantly influence the effective conjugation length. Indeed, long alkyl chains are more flexible and accommodating, such as dodecyl chains, and lead to a larger effective conjugation length than the shorter ones [66,67]. As such, the long alkyl chains at the third position of the thiophene ring, in M4 110 must have favoured effective polymerization, and thus, the conjugation length observed. This value also compares well with those previously obtained by Wang et al. for mesostructured poly(3-dodecylthiophene)-silica composite particles [46]. In situ polymerization leads to a change in color from white for M4110 to a reddish orange for P4, suggesting the formation of conjugated polythiophene chains. UV-vis absorption and fluorescence spectra were recorded to investigate the optical properties of the resulting polythiophene-silica hybrid material P4 (Figure 4). P4 exhibited the maximum absorption and emission wavelengths, at 385 and 582 nm, respectively. Theoretical calculations and experimental measurements have shown that a linear relationship was typically observed between the adiabatic transition energy (E00) and the inverse of the number of thiophene rings, allowing the determination of the effective conjugation length [64,65]. E00 was determined experimentally, by determining the intersection of the normalized absorption and emission spectra. Thus, by exploiting the relationship between E00 and the inverse of the number of thiophene units, the effective conjugation length (ECL) could be estimated. An ECL of ~2.9 nm, corresponding to seven substituted thiophene rings was found from the intersection of the absorption and emission spectra, at 527 nm. The length of alkyl chains at the third position of the thiophene ring, in the polymerization of the thiophene monomers, has been found to significantly influence the effective conjugation length. Indeed, long alkyl chains are more flexible and accommodating, such as dodecyl chains, and lead to a larger effective conjugation length than the shorter ones [66,67]. As such, the long alkyl chains at the third position of the thiophene ring, in M4110 must have favoured effective polymerization, and thus, the conjugation length observed. This value also compares well with those previously obtained by Wang et al. for mesostructured poly(3dodecylthiophene)-silica composite particles [46].

Instrumentation and Methods
Reactions were performed under argon, using oven-dried glassware and Schlenk techniques. 3-(8 -bromooctyl)thiophene was prepared according to the literature procedure [68]. Sodium azide (99.5%), LiAlH 4 (1.0 M in THF), 3-(triethoxysilyl)propyl isocyanate (95%), anhydrous iron chloride (III) (97%) were purchased from Sigma-Aldrich (Saint Louis, MO, USA). Dry DMF and THF were obtained by using a solvent purification system, PureSolve MD5 purchased from Inert Technology (Amesbury, MA, USA). Preparative purifications were performed by silica gel flash column chromatography (Merck ® 40-60 µM, Darmstadt, Germany). Solvents used as eluents were technical grade. IR spectra were recorded on a Perkin Elmer Spectrum 2 FTIR spectrophotometer (Perkin Elmer, Waltham, MA, USA). 1 H, 13 29 Si{ 1 H} was acquired on a Bruker Avance 400 spectrometer (79.46 MHz) (Bruker, Billerica, MA, USA). Mass spectra (MS) were recorded on ESI-TOF Q instruments (Waters, Milford, MA, USA) in the positive mode. Elemental analyses were performed on a Vario MICRO CHNS elemental analyzer (Elementar, LangenselboldGermany). Powder X-ray diffraction experiments were carried out on a high-resolution Bonse-Hart camera with two germanium channel cuts for very small q values (Malvern Panalytical, Worcestershire, United Kingdom). The wavelength used was 1.542 Å (CuK α radiation). Scanning Electron Microscopy (SEM) images were obtained with a Hitachi S2600N microscope (Hitachi, Tokyo, Japan). Transmission Electron Microscopy (TEM) observations were carried out at 100 kV (JEOL 1200 EXII) (JEOL, Tokyo, Japan). Samples for TEM measurements were prepared by embedding the hybrid material in AGAR 100 resin, followed by ultramicrotomy techniques and deposition on copper grids. The solid-state NMR spectrum for 29 Si was recorded on a Varian VNMRS 300 Solid spectrometer (Varian, Palo Alto, CA, USA), at a magnetic field strength of 7.05 T. A 7.5 mm MAS probe was used with a spinning rate of 5 kHz. Single pulse experiments with a continuous wave 1 H decoupling were used for 29 Si NMR, with 2 µs π/2 pulse duration and a recycle delay of 60 s. A recycle delay of 200 s was found necessary to allow a full 29 Si relaxation, although this did not lead to any change in the relative ratio of the individual components on the spectral decomposition. Thus, data with a recycle delay of 60 s could be considered as quantitative. 13 C solid-state NMR analyses were performed on a Varian VNMRS 600 MHz NMR spectrometer (B 0 = 14.1 T, ν 0 ( 1 H) = 599.8MHz and ν 0 ( 13 C) = 150.8MHz). Experiments were performed using a Varian T3 HXY 3.2 mm probe, tuned to 1 H and 13 C, and spinning at 18 kHz. A 1 H-13 C CPMAS (Cross Polarization Magic Angle Spinning) pulse sequence was used, with a 1 H 90 • excitation pulse of 2.5 µs, followed by a ramped contact pulse of 2 ms. Spinal-64 1 H decoupling was applied during acquisition (100 kHz RF). The recycle delay was set to 1-2 s, depending on the sample, and the number of transients acquired ranged from 1430 to 7670. The 13 C chemical shifts were referenced to TMS (tetramethylsilane), using the deshielded resonance of adamantane (38.5 ppm) as a secondary reference.

In Situ Polymerization of Thiophene Groups
Anhydrous iron chloride (III) (0.8 g) and dried chloroform (10 mL) were placed in a round-bottom flask under inert atmosphere. Thiophene-silica composite material (0.3 g) was added and the resulting mixture was stirred, at room temperature for 72 h. The suspension was then filtered and washed with water (2 × 10 mL) and methanol (2 × 10 mL) by centrifugation, and dried under vacuum leading to an orange-red solid.

Conclusions
A new layered polythiophene-silica hybrid material was prepared by hydrolysis and polycondensation of a judiciously-designed, monosilylated-thiophene precursor and its subsequent polymerization. By exploiting the self-assembly of this silylated-thiophene precursor, through van der Waals interactions of alkylene chains, π-stacking interactions between the thiophene units, and hydrogen bonding interactions between ureido groups, a lamellar thiophene-silica hybrid material was achieved. Then, the dense packing of thiophene groups in the central region of the lamellar silica structure allowed the in situ polymerization to form an ordered polythiophene-silica composite. The formation of nanostructured polythiophene-silica was confirmed by combining XRD, TEM, solid-state NMR, and UV-Vis absorption spectroscopy. The UV-Vis absorption and emission spectra of the polythiophene-silica composite in the solid state were very similar to those reported for polythiophene, indicating no significant effect of the silica matrix on the electronic structure of polythiophene. We believe that our strategy represents an efficient approach towards the formation of nanostructured, conjugated, polymers-based hybrid materials with tunable properties, through a judicious design of the silylated monomer.