# Supramolecular polymerization of monomers containing both urea and amide groups: evidence for narcissistic hydrogen bond self-sorting

William Gallonde, Meghana Shekar, Vincent Dorcet, Stéphane Rigaut, Olivier Galangau

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William Gallonde, Meghana Shekar, Vincent Dorcet, Stéphane Rigaut, Olivier Galangau. Supramolecular polymerization of monomers containing both urea and amide groups: evidence for narcissistic hydrogen bond self-sorting. Chemistry - A European Journal, 2025, pp.e202500443. 10.1002/chem.202500443. hal-04975299v2

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# Supramolecular Polymerization of Monomers Containing Both Urea and Amide Groups: Evidence for Narcissistic Hydrogen Bond Self-Sorting

William T. Gallonde,[a] Meghana Shekar,[a] Vincent Dorcet,[a] Stéphane Rigaut,[a] and Olivier Galangau*[a]

In this study, we unambiguously evidence, by mean of UV-Vis and NMR technics supported by theoretical calculations, that a narcissistic H-bond self-sorting takes place during

supramolecular polymerization of a newly designed monomer equipped with mixed urea/amide H-bond donor/acceptor moieties.

## Introduction

Supramolecular polymers (SP), ubiquitous architectures in nature,[1] exhibit many promising features for advanced artificial systems *inter alia* dedicated to optoelectronics,[2] biomedical applications,[3] ferroelectrics,[4,5] charge transport devices,[6] stimuli-responsive materials[7,8] or for enantioselective catalysis purposes.[9] SP may results from the 1D self-assembly of small molecules (the monomers) through a series of weak, reversible and yet directive non-covalent interactions such as, halogen bonds, Van der Waals interactions, π-π stacking, metal-metal interactions or hydrogen bonds to name a few. The latter is usually considered as crucial to construct robust supramolecular architectures.[10,11,12]

While a vast majority of investigations on supramolecular polymers reported on molecules endowed with amide H-bond donor/acceptor moieties, urea functions, well-known to also provide strong H-bonds, were similarly used to construct a wealth of supramolecular materials.[13,14,15,16,17] Alternatively, monomers entailing mixed amide and urea functions were scarcely reported, probably because determining whether the urea (amide) selectively, ie. narcissistically, interacts with urea (amide) functions or if the two functions could mutually form social H-bonds is still very challenging. Meijer and coll.,[18] as well as Raynal and co-workers,[19] suggested that cooperative SP of asymmetrical monomers, endowing the two functions, provide selective Amide-Amide and Urea-Urea interactions (Scheme 1). Unfortunately, despite extensive FTIR studies and neutron scattering investigations combined to theoretical simulations, clear-cut evidence of such narcissistic self-sorting

<figure><img src="image_3.png" /><figcaption>Meijer and coll.</figcaption></figure>

<figure><img src="image_4.png" /><figcaption>Raynal and coll.</figcaption></figure>

**Scheme 1.** Previous examples of “mixed” monomers based on modified BTA motifs, featuring urea and amide groups and exhibiting cooperative supramolecular polymerization.

behavior could not be obtained. Consequently, this lack of characterization drastically impedes the development of new families of monomers and supramolecular polymers taking advantage of both functions.

This lack of knowledge prompted us to investigate the mode of action of H-bond donors/acceptors of such monomers on a simple organic system featuring only one ureido and one amido groups, to gather simple and strong evidences of a social or a narcissist behavior.

For that purpose, absorption spectroscopy represents a valuable technic in the context of the Kasha's excitonic theory[20] to allow discrimination between different type of aggregates and, therefore, between supramolecular packing of different kinds. Consequently, absorption spectroscopy (UV-Visible, CD) has been almost systematically used to investigate supramolecular polymer growth and to identify the corresponding polymerization mechanisms.[21] In this context, a promising strategy would lie in preparing a mixed urea/amide monomer equipped with a chromophoric tag for which dramatically different absorption profiles would arise depending on the narcissistic or social association upon supramolecular aggregation, therefore, resulting in a plain discrimination of the self-sorting situation.

Oligo(phenyleneethynylene)s moieties, termed OPE, represent a valuable class of organic fragments undergoing efficient supramolecular polymerization.[22] Upon stacking, these com-

<footnote>[a] W. T. Gallonde, M. Shekar, Dr. V. Dorcet, Prof. S. Rigaut, Dr. O. Galangau
Univ. Rennes, CNRS, ISCR (Insitut des Sciences Chimiques de Rennes) – UMR
6226 35000 FRANCE
E-mail: olivier.galangau@univ-rennes.fr</footnote>

<footnote>Supporting information for this article is available on the WWW under
https://doi.org/10.1002/chem.202500443</footnote>

<footnote>© 2025 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.</footnote>
<figure><img src="image_5.png" /></figure>

pounds may lead to a large variety of supramolecular aggregates, each of them being characterized by very distinct spectral signatures. With that respect, we recently reported the self-assembly of a small TBA molecule (Figure 1), which is best described as an OPE moiety flanked by two gallic wedges connected by amido linkers (Figure 1). This molecule exhibits, in aliphatic solvents, cooperative kinetically delayed supramolecular polymerization.[23] Upon cooling, this TBA monomer first undergoes a dimerization, identified as a metastable co-facial aggregate where the two transition dipoles for the first absorption transition oriented along the C≡C direction are parallel to each other, leading to a structure-less absorption profile, similar to the monomer (blue line in top part

of Figure 1). This metastable state further evolves into the thermodynamically stable twisted head-to-tail aggregate where the transient dipoles are no longer aligned, yielding a redshifted and well-structured absorption profile relative to the monomer (red line in Figure 1).[23] In other words, TBA displays two very distinct absorption profiles depending on the monomers' orientation within the aggregate.

Hence, it occurred to us that the substitution of one amido linker of TBA by a urea function to lead to TUA (bottom part of Figure 1) should explicitly allow self-sorting determination, in particular with the help of absorption spectroscopy. Indeed, if the monomers self-assemble through narcissistic H-bond self-sorting, the OPE fragment - and transition dipole moment - would align, leading to co-facial arrangement with absorption profile similar to the TBA monomer (blue case). On the contrary, if urea and amide mutually interact through the formation of H-bonds (social H-bond self-sorting), the OPE moieties should form a large angle, which would afford a markedly different absorption profile relative to the TBA monomer (red case).

In the following, we describe the synthesis and the in-depth investigation of the supramolecular aggregation with the help of absorption spectroscopy and NMR experiments, further supported with theoretical calculations, that unambiguously evidences for the first time the existence of narcissistic self-sorting in a urea-amide system.

Previous work

<figure><img src="image_6.png" /></figure>

This work

<figure><img src="image_7.png" /><figcaption>**Figure 1.** (Top) Spectral signatures for TBA. Grey line: absorption profile of the TBA monomer. Blue line: absorption profile of the TBA co-facial aggregate. Red line: absorption profile of the TBA twisted aggregate. (Bottom) Concept for elucidating the narcissistic self-sorting arrangement of H-bonds. With the two hypothetical H-bonds modes of aggregation.</figcaption></figure>

Results and Discussion

**Synthesis of TUA.** TUA was readily obtained in 4 steps (Scheme 2). Starting from compound 1,[24] the amide group was first introduced using standard amidation reaction conditions (DMAP/EDC) to lead to compound 2 in good yields. In parallel, the gallic fragment was converted into the corresponding isonitrile derivative Iso-A₁₂, which was not isolated due to its limited stability, and further condensation with 2 afforded compound 3 displaying the mixed amide-Urea feature, in rather

<figure><img src="image_8.png" /><figcaption>**Scheme 2.** Synthetic route to the targeted compound TUA.</figcaption></figure>
<figure><img src="image_9.png" /></figure>

moderate yield. Then, **TUA** was obtained after trimethylsilyl moiety removal using TBAF as deprotecting agent. All the compounds were thoroughly characterized by ¹H, ¹³C NMR, FTIR spectroscopies and HRMS (see supporting information).

**Investigations of the supramolecular assemblies.** As TBA compound self-assembles into long ribbons in low polarity solvent such as MCH, we investigated **TUA** in MCH at high and low concentrations. At concentrations higher than 2.5 mM, the solutions turned out to be a gel after cooling the sample during 24 h at room temperature. As identified by TEM (Figure 2a), the gelation is due to the formation of a dense network of fibers or ribbons that immobilized the solvent molecules. As seen in Table 1, the critical gelation concentration (CGC) was found similar to that of TBA (2.6 mM) in the same solvent. It is also worth noting that such supramolecular architectures featuring length superior to 5 µm were also identified at C = 22 µM, suggesting anticooperative growth does not operate in this case (vide infra). At such low concentration, the sample is a translucent solution and no longer a gel (Figure 2 b-d). Unexpectedly, **TUA** formed less robust gels compared to TBA as indicated by a lower gel-to-sol transition temperature (Table 1).

Therefore, substituting an amide group by a urea function has a significant impact on gelation process. FTIR spectrum of a **TUA** gel sample (16 mM) displayed characteristic stretching

vibration bands of N–H and C=O bonds at 3308 cm⁻¹, 3253 cm⁻¹ and 1634 cm⁻¹, 1627 cm⁻¹, respectively (Figure 3a). These signals were assigned to urea/amide stretching vibrations involved into strong hydrogen bonds.[18,19] However, at this stage it is not possible to determine whether the H-bonds occurred in a narcissistic or social way, even if the signals at 3253 cm⁻¹ and 1627 cm⁻¹ compared well with the one from **TBA** compound.[23] Nevertheless, these observations indicate that the self-assembly process of **TUA** relies on a dense network of H-bonds.

To get more insights into the structure of these supramolecular polymers, we next investigated the self-assembly mechanism of **TUA** by means of VT-UV/Vis experiments. At high concentration (> 100 µM), upon warming or cooling, we could not witness any sizeable change in the absorption profile, meaning that at such concentration, **TUA** remained fully aggregated at high and low temperatures. However, by lowering the concentration down to 6 µM (Figure 3b), we could observe a significant change of absorption as a function of the temperature. At 90 °C the molecule lied in its monomeric state and featured three absorption bands at 322 nm, 302 nm and 284 nm. Upon cooling the 6 µM hot solution at a rate of 1 K/min, the band at ca. 320 nm saw its intensity decreased and underwent a concomitant sizeable redshift to 325 nm. Lowering the temperature below 25 °C, did not lead to further change in the absorption shape reflecting a high degree of polymerization. Although the absorption variation is weak, it exhibits several pseudo-isobestic points located near 325 nm and 300 nm, indicating a clean equilibrium/transformation between monomer and oligomers/supramolecular polymers.[25] Aging at 25 °C during 18 h did not induce any change in the absorption profile, suggesting the supramolecular polymerization has reached its thermodynamic state (Figure S21). We further calculated the aggregation parameter (α<sub>agg</sub>) at 323 nm and plotted α<sub>agg</sub> as a function of temperature (Figure 3c). Surprisingly, in contrast to **TBA**, a sigmoidal curve emerged indicative of a non-cooperative aggregation, the so-called isodesmic mechanism. Fitting the plotting with the Boltzmann model afforded a corresponding growth enthalpy of ΔH<sub>iso</sub> = −100 kJ/mol and a growth entropic penalty of ΔS<sub>iso</sub> = −234 J/(K.mol). Accordingly, the calculated growth equilibrium constant at 298 K was determined to be K<sub>iso</sub> = 2.10<sup>5</sup> M<sup>−1</sup>, as classically observed for OPE aggregation in non-polar solvents.[22] Upon warming, the disassembly follows an identical process pointing at a thermodynamically controlled polymerization event.

To confirm those unexpected outcomes, we also worked at slightly higher concentration (22 µM) (Figure S20 in SI). Although at the highest temperature we could no longer reach the full disassembled state, we could still observe a sigmoidal absorption profile variation and we were able to determine similar enthalpic and entropic values. Most importantly, the absorption pattern of **TUA** aggregates markedly differs from that observed in our previous report for the thermodynamic state of **TBA** (Figure 4). It is even observed that, **TUA** aggregates absorption spectrum rather matches the one obtained for the kinetic state of **TBA**, where the molecules tend to pack in a cofacial manner with aligned transition dipoles. Therefore, VT-UV/

<figure><img src="image_10.png" /><figcaption>**Figure 2.** a) TEM pictures of a gel of **TUA** in MCH (C = 2.5 mM) showing the formation of a dense network of fibers responsible for the gelation. (Insert: actual photograph of the corresponding gel sample in MCH). b), c) and d) TEM pictures of a diluted solution of **TUA** in MCH (C = 22 µM) at different magnitude.</figcaption></figure>

<table><caption>**Table 1.** Comparative gelation abilities of **TUA** and **TBA** in MCH.</caption><thead><tr><th></th><th>CGC (mM)</th><th>Tgel/sol (°C)</th><th>Ref.</th></tr></thead><tbody><tr><td>TBA</td><td>2.6</td><td>45</td><td>[23]</td></tr><tr><td>TUA</td><td>2.5</td><td>34</td><td>This work</td></tr></tbody></table>
<figure><img src="image_11.png" /></figure>

<figure><img src="image_12.png" /><figcaption>**Figure 3.** a) FTIR spectrum of a gel sample of TUA in MCH (16 mM). b) Variation of the absorption profile of a 6 µM solution of TUA in MCH. c) Aggregation parameter (calculated at 323 nm) plot as a function of temperature. d) Solvent induced denaturation experiment monitored by ¹H NMR, showing the chemical shift variation of alkyne proton and methyl protons of TUA upon increasing the amount of good solvent (THF).</figcaption></figure>

<figure><img src="image_13.png" /><figcaption>**Figure 4.** Comparison between the as-found absorption profile of TUA and the two spectral signatures of TBA stacking modes in MCH.</figcaption></figure>

vis experiments clearly indicate that TUA adopts a co-facial packing, synonymous of a narcissistic H-bond self-sorting.

We attempted to obtain further insights into the supramolecular packing by monitoring the change of TUA ¹H NMR spectrum upon solvent-induced denaturation experiment, where THF was used as good solvent for the molecule (Figure 3d). Such a technique was successfully applied by others to investigate the disassembly of artificial supramolecular polymers.[26] At 100% MCH content, the molecules are NMR silent, diagnostic of efficient aggregation in solution. Addition of small amount of THF triggered partial disassembly with concomitant appearance of new a set of molecular signals. More precisely, upon addition of 10 vol% THF, a singlet emerged at c.a. 3.0 ppm, which was assigned to the alkyne proton. As the vol% of THF increases, this singlet is downfield shifted up to 3.5 ppm. This suggests that in the aggregate state, the alkyne proton is most likely strongly shielded by a π system. Similar observations and conclusion can be made for the singlet signal assigned to the methyl protons which shifts from 2.1 ppm to almost 3.0 ppm at 100 vol% THF. The simultaneous upfield shifting for these signals strikingly contrast with our previous results on TBA. Indeed, upon thermal disassembling of TBA thermodynamic state (where transition dipoles are non-
<figure><img src="image_14.png" /></figure>

aligned), no chemical shift variation of the alkyne proton signal was observed while the methyl protons experienced upfield shifting. These experimental results are in line with the spectroscopic outcomes, describing well a face-to-face supramolecular packing, similar to J-aggregate, where the π systems are slightly staggered with clear alignment of their OPE fragments (and of their transition dipole moments).

**Theoretical investigations.** We eventually supported these findings with the help of theoretical simulation of the supramolecular packing. Calculations were performed at the B3LYP/6-31G(d,p)-D3 level of theory. Although aliphatic chains should contribute to a limited extend through VdW interactions to the overall packing stability, they were replaced by methoxy groups to reduce computational cost. In the past, several groups including ours have obtained reliable results following this approach.[23,27] After optimizing the monomeric structure, we calculated dimers of TUA with various configurations. We constructed two possible supramolecular packing, namely the face-to-face (FTF) one where transition dipoles are aligned and the head-to-tail (HTT) one where the transition dipoles form a large angle. For each packing, two H-bond arrangements were further discriminated whether they displayed narcissistic H-bond self-sorting (indexed with -NA) or social H-bond self-sorting (indexed with -SO) (Figure 5a and Figure S23). At first sight, dimer FTF-SO features the upper monomer with C=O groups pointing toward the same direction. Such a molecular arrangement likely prohibits polymeric growth and cannot account for our experimental observations. Therefore, FTF-SO was quickly abandoned for the rest of the discussion. Among the three remaining possibilities (FTF-NA, HTT-NA and HTT-SO), FTF-NA was predicted to be the most stable by 22 kJ/mol (17 kJ/mol) relative to HTT-NA (HTT-SO). Accordingly, Boltzmann population calculation afforded a 99.9% population of FTF-NA dimer arrangement at room temperature. Importantly, in this arrangement, the two OPE moieties adopt a co-facial configuration (Figure 5) with a slight offset of the OPE moieties along the C=C direction, akin to J-aggregate arrangements. As a result, both the methyl and the alkyne protons face the π systems of the neighboring molecule, in line with the NMR observations.

However, the sole narcissistic H-bonds self-sorting arrangement cannot explain the increased stability of FTF-NA stacking against HTT-NA, since both structures feature comparable H-bonds distances (Table S3). We anticipated that series of complementary dispersive interactions not present in HTT-NA should contribute to the stabilization of FTF-NA relative to HTT-NA. To clarify this, we calculated the non-covalent interactions on a dimeric structure adopting the FTF-NA packing (Figure 5b). Accordingly, dispersive forces (dark-blue surfaces) likely occur between the OPE fragments, the toluene moieties and the two gallic wedges. These results match well with the as-calculated intermolecular distances characteristic of weak π-π stacking (intermolecular distance of 3.7 Å) and CH-π interactions (distances ranging from 2.5 to 2.7 Å), respectively. The rather high intermolecular distance probably accounts for the weak exciton coupling, which results in a slight modification of the absorption signature relative to the monomeric state.

<figure><img src="image_15.png" /><figcaption>**Figure 5.** a) Presentation of the four dimer configurations: FTF-NA, FTF-SO, HTT-NA and HTT-SO. Upper molecules are light pink coloured while lower molecules are light blue coloured. In HTT-SO, the two H-bond donor/acceptor groups of the upper molecule are oriented downward which likely prevents further growth. b) DFT calculated FTF-NA dimeric structure showing the J-aggregate. The methyl and the acetylene protons (highlighted in orange) face an aromatic system, likely inducing a magnetic shielding of their resonance. The alkoxy groups were replaced by OMe to limit computational cost. c) Calculated non-covalent interactions (NCI) (dark blue surfaces, isovalue = 0.67) in FTF-NA dimer, highlighting the secondary interactions likely stabilizing the co-facial staggered J-aggregate stacking. The hydrogen atoms were omitted for clarity.</figcaption></figure>

Eventually, we computed the stabilization energy in the dimer with respect to the monomer, and in trimer with respect to the dimer using the Face-to-Face narcissistic self-sorting packing. We found a stabilization energy of –251 kJ/mol
<figure><img src="image_16.png" /></figure>

(-254 kJ/mol) for the dimer (trimer) formation. Although these values seem unrealistic, one should note that our simulations do not account neither for the solvent influence nor for the impact of long aliphatic chains. However, importantly, these finding highlight that the aggregate growth is characterized by a constant stabilization energy, as defined for an isodesmic model, matching well with the experimental findings. Altogether, DFT calculations reliably reproduced the experimental data, strongly supporting that TUA monomers self-assemble through a balanced combination of weak dispersive interactions on one side and narcissistic H-bonds on the other. Because the resulting co-facial packing represents the most stable supramolecular arrangement, the process becomes downhill, explaining the isodesmic growth and accounting for the vanishing of the cooperativity with respect to the TBA polymerization process.

## Conclusions

In this work, we have investigated the self-assembly properties of a novel monomer equipped with urea and amide functions. Our original approach using absorption spectroscopy and NMR confirmed the assumptions of Meijer et al. and Raynal et al yielding for the first time concrete experimental evidences of narcissistic H-bonds self-sorting. In addition, DFT simulations strongly support the narcissistic self-sorting situation and highlights the key supramolecular interactions accounting for the observed self-assembly mechanism. Overall, this study opens new perspectives regarding programmable construction of supramolecular polymers.

## Supporting Information

The authors have cited additional references within the Supporting Information (Ref. [24,28–31]). The Supporting Information includes the synthetic details, FTIR measurements, a full view of the NMR monitoring of the solvent mixing experiment, complementary VT-UV/Vis measurements.

## Acknowledgements

The authors thank the THEMIS Platform (ScanMAT-UAR2025) for TEM facilities access. The authors thank the Université de Rennes, Rennes Métropôle, the CNRS and the ANR (SAMAT, ANR-21-CE06-0012-01).

## Conflict of Interests

The authors declare no conflict of interest.

## Data Availability Statement

The data that support the findings of this study are available from the corresponding author upon reasonable request.

**Keywords:** Supramolecular polymer • isodesmic growth • amide-urea narcissistic self-sorting • variable temperature experiment • transition dipole moment

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Manuscript received: February 6, 2025

Accepted manuscript online: February 11, 2025

Version of record online: ■■, ■■
RESEARCH ARTICLE

We report how with simple spectro-
scopic technic we could obtain clear
evidence of narcissistic H-bonds self-
sorting during supramolecular poly-
merization of a judiciously designed
monomer endowing urea and amide
functions.

<figure><img src="image_18.png" /></figure>

W. T. Gallonde, M. Shekar, Dr. V. Dorcet,
Prof. S. Rigaut, Dr. O. Galangau*

1 – 8

Supramolecular Polymerization of
Monomers Containing Both Urea
and Amide Groups: Evidence for Nar-
cissistic Hydrogen Bond Self-Sorting

<figure><img src="image_19.png" /></figure>