# Self-Assembly of Hydrogen-Bonded Organic Crystals on Arbitrary Surfaces for Efficient Amplified Spontaneous Emission

Yuliya Kenzhebayeva, Irina Gorbunova, Arthur Dolgopolov, Maksim V Dmitriev, Timur Sh Atabaev, Evgeniia A Stepanidenko, Anastasiia S Efimova, Alexander S Novikov, Sergei Shipilovskikh, Valentin A Milichko

► To cite this version:

Yuliya Kenzhebayeva, Irina Gorbunova, Arthur Dolgopolov, Maksim V Dmitriev, Timur Sh Atabaev, et al. Self-Assembly of Hydrogen-Bonded Organic Crystals on Arbitrary Surfaces for Efficient Amplified Spontaneous Emission. Advanced Photonics Research, 2023, 5 (2), pp.2300173. 10.1002/adpr.202300173. hal-04974286

HAL Id: hal-04974286

https://hal.science/hal-04974286v1

Submitted on 3 Mar 2025

HAL is a multi-disciplinary open access
archive for the deposit and dissemination of sci-
entific research documents, whether they are pub-
lished or not. The documents may come from
teaching and research institutions in France or
abroad, or from public or private research centers.

L'archive ouverte pluridisciplinaire HAL, est
destinée au dépôt et à la diffusion de documents
scientifiques de niveau recherche, publiés ou non,
émanant des établissements d'enseignement et de
recherche français ou étrangers, des laboratoires
publics ou privés.

<figure><img src="image_1.png" /></figure>

Distributed under a Creative Commons Attribution 4.0 International License
# Self-Assembly of Hydrogen-Bonded Organic Crystals on Arbitrary Surfaces for Efficient Amplified Spontaneous Emission

Yuliya Kenzhebayeva, Irina Gorbunova, Arthur Dolgopolov, Maksim V. Dmitriev, Timur Sh. Atabaev, Evgeniia A. Stepanidenko, Anastasiia S. Efimova, Alexander S. Novikov, Sergei Shipilovskikh,* and Valentin A. Milichko*

Organic lasers attract much attention due to their high efficiency, low energy consumption, and structural flexibility. However, long-term stability and the creation of the lasers on arbitrary surfaces remain a challenge. Here, a synthesis of amide-based organic molecules that provides packing into hydrogen-bonded organic crystals (OCs) is reported. The resulting OCs demonstrate an amplified spontaneous emission (ASE) regime with 0.55 µJ cm⁻² threshold under the normal conditions due to 5%–13% quantum yield and high emission rate (1.02 ns). The simple process of self-assembly of the hydrogen-bonded OCs and highly stable ASE (over 30 min of continuous operation) allow fabricating fibers, flexible polymers, and hard planar periodic optical systems based on them, which paves the way to creating organic laser diodes of an arbitrary design.

## 1. Introduction

Since the discovery of conductive polymers,[1a] organic solar absorbers,[1b] and laser dyes,[1c] organic solids have a special place among the materials for micro- and optoelectronic applications. Compared to most of their inorganic counterparts, the low cost and simple liquid-phase manufacturing of organic solids are accompanied

with high efficiency of operation and clean energy transition.[2] Along with the chemical composition, the intermolecular interactions directly determine the functionality of the organic solids through the managing of molecule packing into a crystal. An increase of this energy leads to a change in the electronic structure of the crystal compared to a single molecule,[3a,b] which opens up the possibility to tune the optical, electronic, and transport properties of the resulting organic crystal (OC). However, such strong intermolecular interactions ensure an efficient charge transfer between the structural elements of the OC, which in turn can degrade the photoemission properties via

the quenching process.[3f,k] On the contrary, a decrease in this energy by introducing hydrogen bonds[3c-e] preserves the electronic features of individual molecules and their photoemission properties, as well as expands the fashion of molecular packing and provides the control of the OC growth on arbitrary surface. In turn, these are of fundamental importance to easily produce efficient sources of coherent and incoherent light.[1c]

Y. Kenzhebayeva, I. Gorbunova, A. Dolgopolov, A. S. Efimova, S. Shipilovskikh
School of Physics and Engineering
ITMO University
St. Petersburg 197101, Russia
E-mail: s shipilovskikh@metalab.ifmo.ru

E. A. Stepanidenko
International Research and Educational Center for Physics of
Nanostructures
ITMO University
St. Petersburg 197101, Russia

I. Gorbunova, M. V. Dmitriev, S. Shipilovskikh
Department of Chemistry
Perm State University
Perm 614990, Russia

T. S. Atabaev
Department of Chemistry
Nazarbayev University
Astana 010000, Kazakhstan

A. S. Novikov
Institute of Chemistry
Saint Petersburg State University
St. Petersburg 199034, Russia

A. S. Novikov
Research Institute of Chemistry
Peoples' Friendship University of Russia (RUDN University)
Moscow 117198, Russia

V. A. Milichko
Institut Jean Lamour
Université de Lorraine
CNRS
F-54000 Nancy, France
E-mail: valentin.milichko@univ-lorraine.fr

The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adpr.202300173.

© 2023 The Authors. Advanced Photonics Research 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.

DOI: 10.1002/adpr.202300173
Among the large family of organic solids, special attention is paid to the OCs, whose structure is balanced by hydrogen bonding.[³c-e] Possessing excellent liquid-phase self-assembly, managed by external stimuli,[⁴] as well as flexible low-energy hydrogen bonds, the resulting OCs offer novel solids of desired molecular packing, crystal shapes, and environmental stability[⁵] for optical application. Indeed, hydrogen-bonded OCs exhibit structure-driven white light emission,[⁶a] photoluminescence,[⁶b] terahertz generation and detection,[⁶c] nonlinear optical absorption,[⁶d,e] light-controlled phase transitions,[⁶f,g] as well as amplified spontaneous emission (ASE)[⁷] and even lasing.[⁴a,b,7d] However, compared to a big family of optically active OCs, also possessing ASE[⁸] and lasing effects (Table S4, Supporting Information),[⁹] the stable and highly efficient operation of the hydrogen-bonded OCs are yet in their infancy.

Here we report on the liquid-phase self-assembly of OCs based on ethyl 2-((1-((adamantan-1-yl)amino)-4-(4-methoxyphenyl)-1,4-dioxobut-2-en-2-yl)amino)-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate molecules packed into a single crystal of centrosymmetric space group *P*2₁/*c*. Structural analysis, numerical modeling, and optical spectroscopy confirmed the hydrogen nature of molecular packing, which ensures the optical absorption and photoluminescence (PL) of individual molecules packed into a single crystal. An efficient PL (5%–13%) with high relaxation time (1.02 ns), as well as regular geometric shape allow observing ASE with a threshold of 0.55 µJ cm⁻² at ambient conditions. An endurance of the obtained crystals during ASE

regime, confirmed during 30 min of continuous operation, together with the crystal growth on arbitrary surfaces such as flexible polymer substrates, periodic silicon structures, and optical fibers, opens the way to the easy fabrication of scalable coherent light sources.

## 2. Results and Discussion

### 2.1. Synthesis

Substituted derivatives of Gewald's 2-aminothiophenes have been chosen as model structural units to build the OC with promising optical properties. In fact, such compounds have been successfully utilized for the synthesis of the OCs possessing efficient optical absorbance and emission.[10a-g] Moreover, their low toxicity and high biocompatibility[10h,i] make them perspective also for “green” optoelectronics.

To obtain the OCs based on ethyl 2-((1-((adamantan-1-yl)amino)-4-(4-methoxyphenyl)-1,4-dioxobut-2-en-2-yl)amino)-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate (amide 9) containing Gewald's aminothiophene groups (see Scheme 1), we have performed the following multistep synthesis. First, the key starting intermediates such as ethyl 2-amino-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate (Gewald's aminothiophene) 6 and 2-hydroxy-4-(4-methoxyphenyl)-4-oxobut-2-enoic acid 3 have been obtained (Scheme 1). We have included an electron-donating flexible aliphatic cyclohexane substituent in the fourth and fifth

<figure><img src="image_2.png" /><figcaption>**Scheme 1.** Synthetic steps of ethyl 2-((1-((adamantan-1-yl)amino)-4-(4-methoxyphenyl)-1,4-dioxobut-2-en-2-yl)amino)-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate 9.</figcaption></figure>
<figure><img src="image_3.png" /><figcaption>**Figure 1.** a) Crystal structure of the OC and its optical image. Scale bar, 50 µm. b) Absorption (red curve) and PL (blue curve) spectra for single OC and the solution of the molecules 9 in DMF (concentration of 0.5 mg ml⁻¹). c,d) Shape and energies of frontier molecular orbitals in the OC and the total DOS (TDOS). e) Hirshfeld surface of the OC, demonstrating the predominant contribution of hydrogen interactions (see also Figure S13, Supporting Information).</figcaption></figure>

position of the Gewald's aminothiophene 6 structure, as well as an electron-withdrawing -COOEt substituent in the third position of the thiophene ring. Also, an electron-donating group as -OMe has been included into the paraposition of the aromatic ring of the structure of 3. On the first step, 3 has been synthesized by the Claisen condensation method via the reaction of diethyl oxalate 2 with 1-(4-methoxyphenyl)ethan-1-one 1 in the presence of sodium methoxide in methanol, with subsequent decomposition of the intermediate salt. Then, Gewald's aminothiophene 6 has been obtained by the reaction of the corresponding cyclohexanone 4 with ethyl 2-cyanoacetate 5 and sulfur in the one-pot method. The next step included the interaction of 3 and 6 in ethanol at 60 °C resulting in 2-((3-(ethoxycarbonyl)-4,5,6,7-tetrahydrobenzo[b]thiophen-2-yl)amino)-4-(4-methoxyphenyl)-4-oxobut-2-enoic acid 7. The intramolecular cyclization of 7 in the presence of propionic anhydride led to obtaining ethyl 2-((5-(4-methoxyphenyl)-2-oxofuran-3(2H)-ylidene)amino)-

4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate 8. Finally, the ring opening of 8 by the reaction with 1-aminoadamantane provided the formation of ethyl 2-((1-((adamantan-1-yl) amino)-4-(4-methoxyphenyl)-1,4-dioxobut-2-en-2-yl)amino)-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate (amide) 9. The inclusion of the substituent of the 1-aminoadamantane type in the structure of the resulting OC (see below) made it possible to increase the volume of the unit cell and the structural flexibility of the molecule.

Then, the OC based on 9 have been grown from the solution of acetone, acetonitrile, or dimethylformamide (DMF). Based on single-crystal X-Ray diffraction analysis (SCXRD), the crystal structures in all three cases are identical (Figure 1a, S1–S3, Supporting Information): the centrosymmetric space group *P*2₁/*c* of the monoclinic system with one molecule in the asymmetric unit. In detail, the molecule 9 adopts planar conformation, while the carboxamide moiety turned at a large angle to the planar
part of the compound. The planar shape can be explained by π-electron conjugation and the three-centered intramolecular hydrogen bond between the amino group and two oxygen atoms of ketone and ester carbonyls [N–H···O 2.07(3) Å and 2.09(3) Å]. In the resulting OC, the molecules 9 are linked into centrosymmetric dimers (Figure S4, Supporting Information) via hydrogen bonds (Figure 1e) between the amide NH group and the ketone carbonyl [N–H···O 2.30(3) Å]. In this dimer, the molecules are arranged in an antiparallel manner, while the thiophene and aryl rings are close to each other. Nevertheless, the large distance between them (3.6–3.8 Å) indicates that π–π interactions are relatively weak (Figure S4, Supporting Information). The adjacent dimers are organized in a slip-stacked structure. The absence of strong π–π stacking interactions and the presence of several short C–H···O and C–H···H bonds between adjacent stacks involving aliphatic hydrogen atoms of the adamantyl and cyclohexane moieties play an important role in maintaining the PL of the resulting OC (see below). Finally, the resulting OCs possess a rectangular shape with an average aspect ratio of 100 × 500 µm (Figure 1b) and a height of 2.5 µm (Figure S6, Supporting Information).

2.2. Modeling

Based on structural analysis, we have performed numerical
modeling using the density functional theory (DFT) to confirm
the molecular packing driven by hydrogen bonding, as well as to

predict the optical properties of the resulting OCs (Figure 1c-e, and Figure S7-S12, Supporting Information). DFT revealed that the presence of neighboring molecules 9 insignificantly affects the density-of-state (DOS) spectra and the PL of the OCs as well (see below). Moreover, based on the Hirshfeld surface analysis (Figure 1e, S13, S14, Supporting Information), we confirmed that the adamantan part of the molecule 9 contributed significantly to the packing of the molecules into the OC via hydrogen interactions.

**2.3. Optics**

Optical transmission spectroscopy confirmed the DFT results. As shown in Figure 1b, S15 (Supporting Information), the single OCs are optically transparent with an estimated bandgap of 2.3 ± 0.1 eV. Herein, both the single OC and the solution of the molecule 9 in DMF demonstrate similar optical absorption behavior. This correlates well with the structural and DFT data predicting the hydrogen interaction between the packed molecules. In turn, this interaction prevents the electron transfer between the molecules 9 and explains the agreement between the absorption spectra of the OC and the molecule solution.

An excitation of both the single OC and the molecule solution by 3.55 eV photons (350 nm, see Experimental Section) stimulated an efficient photoexcitation of electrons between the allowed energy states (Figures S7–S12, Supporting Information), leading to an intense PL signal. Herein, the PL of the OC is centered

<figure><img src="image_4.png" /><figcaption>**Figure 2.** a,b) Evolution of the PL from single OC upon the 350 nm (150 fs, 80 MHz) laser radiation of varied fluence (from 0.01 to 0.9 µJ cm⁻²). c) Confocal Raman analysis of the OC before and after the action of 350 nm (laser fluence of 0.7 µJ cm⁻²). d) Time-resolved PL measurements for the OC and the solution of molecules 9 in DMF, as well as e) the fluorescence lifetime imaging microscopy of the OC performed on a confocal microscope MicroTime 100 (PicoQuant) equipped with an objective (40×/0.65 NA) and laser source of 405 nm (5 MHz, 70 ps). f) PL quantum yield analysis for the powder of OCs (red dot at 350 nm corresponds to the QY of the solution of molecules 9 in DMF with the concentration of 0.5 mg ml⁻¹). Red arrow indicates the wavelength of pumping laser light for ASE regime (Figure 3).</figcaption></figure>
at 565 nm, while the molecule solution demonstrates PL at 533 nm
with the same (100 nm) full width at half maxima (FWHM).

A detailed study of the PL showed the following (Figure 2). During excitation by 350 nm (150 fs pulse duration, 80 MHz repetition rate) of a varied laser fluence (0.01 to 0.9 µJ cm⁻²), we detected a linear increase of the PL intensity without changing the FWHM (Figure 2a,b). A further increase in the laser fluence (from 0.7 µJ cm⁻²) led to deviation from the linear slope and the irreversible PL intensity drop. Such behavior has been also analyzed by confocal Raman spectroscopy: As shown in Figure 2c, the positions of the Raman peaks and the ratio of intensities were maintained, while the intensity of the Raman peaks dropped upon the action of laser radiation with 0.7 µJ cm⁻² fluence. This can be explained by the thermal decomposition of the OCs under the action of laser radiation, which possibly heats the OC above the decomposition temperature (see thermogravimetric data in Figure S5, Supporting Information) due to almost 100% absorption at 350 nm. In addition, the measurement of the PL decay showed that the single OC re-emits photons quite fast (1.02 ns compared to 1.4 ns for the solution, see Figure 2d, S18, Supporting Information), while the PL emission mapping demonstrated the homogeneous PL decay time over the OC surface (Figure 2e, Supporting Information).

2.4. ASE

An analysis of the quantum yield (QY) for the OCs showed that the QY value varies from 5% for 400 nm laser pump to 13% for 260 nm (Figure 2f),[11] which is possibly due to an increase in the absorption coefficient in the ultraviolet region. These results

made it possible to estimate the radiative (k<sub>r</sub>) and nonradiative
decay rates (k<sub>nr</sub>). According to the definition of &tau; = 1/(k<sub>r</sub> + k<sub>nr</sub>)
and &phi; = k<sub>r</sub>/(k<sub>r</sub> + k<sub>nr</sub>),<sup>[1c]</sup> where &tau; is PL decay time (1.02 ns in
our case) and &phi; is the PL QY (0.058 for 350 nm laser pump,
Figure 2f), we obtained the values of k<sub>r</sub> = 0.057 ns<sup>-1</sup> and k<sub>nr</sub> =
0.92 ns<sup>-1</sup>. Despite the fact that the nonradiative decay rate is 16
times higher than k<sub>r</sub>, a regular geometric shape of the OC
and a relatively high thermal stability (Figure S5, Supporting
Information) should ensure the transition from the PL to ASE
regimes. To prove it, we have utilized 354 nm laser pump at a
low repetition rate (see Experimental Section). Figure 3a demon-
strates that with an increase in the laser fluence (0.55 &mu;J cm<sup>-2</sup>)
threshold, Table S4, Supporting Information), the PL intensity
grows nonlinearly with a parallel decrease in FWHM (Figure 3b):
6-fold narrowing of the PL spectrum (Figure S19, Supporting
Information) and 15-fold increase in its intensity directly indicate
the ASE regime.[3] Important is that the endurance of ASE
regime has been confirmed during 30 min of continuous photo-
emission (with 4% error) at ambient conditions (Figure 3d).

We have also estimated the gain parameter of the OCs: The Q factor, describing an ability of any feedback material to retain light, can be expressed as $Q = \lambda_r / \Delta\lambda$, where the resonance wavelength $\lambda_r$ corresponds to ASE maximum (600 nm in our case), and $\Delta\lambda$ is the FWHM value (14 nm in our case, see Figure S19, Supporting Information). In our case Q equals 42, which is not enough for lasing,[1c] but still meets the criteria for creating the laser diodes.

Finally, taking into account the simple process of self-assembly
of the hydrogen-bonded OCs and their promising thermal and
optical properties, we assumed that the OC could serve as an effi-
cient optical emitter not only as independent objects but also as

<figure><img src="image_5.png" /><figcaption>**Figure 3.** a,b) ASE regime achieved by the 10 ps laser pump (354 nm). c) Optical image of the OC at ASE regime. Scale bars, 50 µm. d) Endurance of ASE regime in OC under the action of 0.6 µJ cm⁻² laser fluence (354 nm).</figcaption></figure>
<figure><img src="image_6.png" /><figcaption>**Figure 4.** Self-assembly of the OC onto a) flexible polymer substrate, b,c) optical fiber, and d) periodic silicon structure, with corresponding e–g) PL/ASE spectra. Scale bars, 1 cm (a,b), 50 µm (c,d).</figcaption></figure>

an integrated part of the optical systems. To check our assumption we have performed the OC self-assembly on different surfaces such as flexible polymer substrates (Figure 4a), optical fibers (Figure 4b,c), and periodic silicon structures (Figure 4d). As can be seen from the corresponding PL and ASE spectra (Figure 4e–g), the OC crystals demonstrate efficient PL/ASE under normal conditions on any surfaces. Herein, no any crumbling or degradation of the OCs during several weeks of continuous operation can be detected.

3. Conclusion

We report on a multi-step synthesis of amide-based organic molecules (ethyl 2-((1-((adamantan-1-yl)amino)-4-(4-methoxyphenyl)-1,4-dioxobut-2-en-2-yl)amino)-4,5,6,7-tetrahydrobenzo [b]thiophene-3-carboxylate (amide)) which can be packed into OCs with hydrogen bonding. The resulting OCs possess an ASE under normal conditions with 5%–13% QY, 0.55 µJ cm⁻² threshold, and high emission rate (1.02 ns). Such promising optical properties together with high thermal stability allow us to observe ASE regime for 30 min, avoiding the OC degradation. Finally, the simple process of self-assembly of the OCs on optical fibers, flexible polymer substrates, and hard planar optical systems paves the way to creating efficient laser sources of an arbitrary design.

4. Experimental Section

*Materials:* All the chemical reagents were purchased from commercial sources and used without further purification unless otherwise specified. The synthesis and NMR analysis of the molecules are described in detail in Supporting information.

**Single-Crystal X-Ray Diffraction:** The unit cell parameters and the X-Ray diffraction intensities were measured on a Xcalibur Ruby diffractometer.

The empirical absorption correction was introduced by a multiscan method using SCALE3 ABSPACK algorithm. Using Olex2, the structures were solved with the SHELXT or olex2-solving programs and refined by the full-matrix least-squares method in the anisotropic approximation for all nonhydrogen atoms with the SHELXL program. Hydrogen atoms bound to carbon were positioned geometrically and refined using a riding model. The hydrogen atoms of NH groups were also refined independently with isotropic displacement parameters. The structures were refined using HKLF5 format file as twins with two components. CCDC numbers: 2262701, 2262703, 2262702.

**Optical Transmittance:** For the transmittance spectra measurements, the OCs were irradiated with a white halogen lamp of 360–2500 range (Avantes). The light was focused with an objective (Mitutoyo 10×/0.28 NA) and further the signal was collected by an objective (Mitutoyo 50×/0.42 NA). The transmittance response was analyzed with a HORIBA LabRAM confocal spectrometer with a water-cooled charge-coupled device (CCD, Andor DU 420A-OE 325) with 150 g mm⁻¹ diffraction grating.

**Raman Spectroscopy:** For the Raman scattering spectra measurements, the OCs were irradiated by a He–Ne laser with 632.8 nm wavelength in a confocal LabRAM HR Horibo system. Laser radiation was focused with an objective (Mitutoyo 100×/0.9 NA), collected, and analyzed by confocal Horiba LabRan spectrometer (1800 g mm⁻¹ diffraction grating).

**Photoluminescence:** For the PL measurements, the OCs were irradiated with the third harmonic of femtosecond laser with 1050 nm central wavelength (Yb³⁺ active medium, TeMa, Avesta Project, a pulse length of 150 fs, a repetition rate of 80 MHz). The laser radiation was focused with an objective (NUV Mitutoyo 20×/0.4 NA). The PL signal was collected with the objective (Mitutoyo 50×/0.42 NA) and then analyzed with a Horiba LabRan confocal spectrometer with a water-cooled CCD (Andor DU 420A-OE 325) with 150 g mm⁻¹ diffraction grating.

**Amplified Spontaneous Emission:** For the ASE regime spectra measurements, single OCs were irradiated with third-harmonic EKSPLA PL2140, Nd:YAG laser with 1064 nm central wavelength (and 354 nm as a third harmonic). The laser repetition rate was 10 Hz with 27 ps impulse duration. Laser radiation was focused with an objective (20×/0.4 NA), while ASE signal was detected with Avantes spectrometer and then analyzed. The intensity of laser radiation was varied from 0.1 to 1 µJ cm⁻².

**PL Lifetime:** Time-resolved PL measurements were performed on a confocal microscope MicroTime 100 (PicoQuant) equipped with an objective (40×/0.65 NA) and a 405 nm pulsed diode laser. The laser repetition
rate was 5 MHz. The fluorescence lifetimes were determined by two-component analysis using the n-exponential reconvolution-fitting function of the SymPhoTime (PicoQuant) software for the fluorescence decay curve.

**Atomic Force Microscopy (AFM):** The AFM scans were done by SmartSPM 1000 (AIST-NT microscope) in semicontact mode at ambient conditions. Working cantilevers were PPP-NCSTAuD-10 (Nanosensors) made with highly doped silicon with Au coating on detector side, resonant working frequency of 140 kHz, and force constant 14 N m⁻¹ with 7 nm tip radius.

**DFT:** The total DOS and frontier molecular orbitals for model system based on the experimental X-Ray geometry were calculated at the DFT level of theory using the dispersion-corrected hybrid functional ωB97XD with the help of Gaussian-09 program package and Multiwfn program (version 3.7). The segmented contracted error-consistent basis sets x2c-TZVPall of triple-ζ valence quality for relativistic all-electron calculations were used for all atoms. The Hirshfeld molecular surface was generated by CrystalExplorer program (version 17.5). The normalized contact distances, *d*<sub>norm</sub>, based on Bondi's van der Waals radii, were mapped into the Hirshfeld surface.

**Quantum Yield Measurements:** The QY of prepared samples was measured using an absolute quantum yield spectrometer (C11347-11, Hamamatsu Photonics K.K.) in automated scanning mode (5 nm step). All measurements were performed at room temperature.

**Supporting Information**

Supporting Information is available from the Wiley Online Library or from the author.

**Acknowledgements**

V.A.M., Y.K., and A.S.E. acknowledge the support by the Russian Science Foundation (grant number 22-72-10027 "Flexible hybrid materials as active layer in memory devices" for the optical part) and Priority 2030 Federal Academic Leadership Program. S.A.S. acknowledges the support by the Russian Science Foundation (grant number 22-73-10069 "Design and application of flexible Metal organic frameworks for photonics devices" for the chemical part). A.S.N. acknowledges the support within RUDN University Strategic Academic Leadership Program.

**Conflict of Interest**

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**

amides, amplified spontaneous emission, nonlinear optics, organic crystals, self-assembly

Received: June 4, 2023

Revised: August 31, 2023

Published online: November 10, 2023

[1] a) Z. Bao, J. Locklin, S. I. Stupp, Nat. Mater. **2020**, *19*, 922; b) J. Hou, O. Inganäs, R. Friend, F. Gao, Nat. Mater. **2018**, *17*, 119; c) A. J. C. Kuehne, M. C. Gather, Chem. Rev. **2016**, *116*, 12823.

[2] a) S. Carley, D. M. Konisky, Nat. Energy **2020**, *5*, 569; b) N. Dean, Nat. Energy **2022**, *7*, 785; c) F. Guo, B. J. van Ruijven, B. Zakeri, S. Zhang, X. Chen, C. Liu, F. Yang, V. Krey, K. Riahi, H. Huang, Y. Zhou, Nat. Energy **2022**, *7*, 1144; d) N. Kulachenkov, M. Barsukova, P. Alekseevskiy, A. A. Sapianik, M. Sergeev, A. Yankin, A. A. Krasilin, S. Bachinin, S. Shipilovskikh, P. Poturaev, N. Medvedeva, E. Denislamova, P. S. Zelenovskiy, V. V. Shilovskikh, Y. Kenzhebayeva, A. Efimova, A. S. Novikov, A. Lunev, V. P. Fedin, V. A. Milichko, Nano Lett. **2022**, *22*, 6972; e) N. Kulachenkov, Q. Haar, S. Shipilovskikh, A. Yankin, J.-F. Pierson, A. Nominé, V. A. Milichko, Adv. Mater. **2022**, *32*, 2107949.

[3] a) N. J. Hestand, F. C. Spano, Chem. Rev. **2018**, *118*, 7069; b) S. Ma, S. Du, G. Pan, S. Dai, B. Xu, W. Tian, Aggregate **2021**, 2, e96; c) J. Donohue, J. Phys. Chem. **1952**, *56*, 502; d) E. D. Głowacki, M. Irimia-Vladu, S. Bauer, N. S. Sariciftci, J. Mater. Chem. B **2013**, *1*, 3742; e) R.-B. Lin, Y. He, P. Li, H. Wang, W. Zhou, B. Chen, Chem. Soc. Rev. **2019**, *48*, 1362; f) S. Muduli, P. Pandey, G. Devatha, R. Babar, M. Thripuranthaka, D. C. Kothari, M. Kabir, P. P. Pillai, S. Ogale, Angew. Chem., Int. Ed. **2018**, *57*, 7682; g) N. V. Baidus, A. Chahboun, M. J. M. Gomes, M. I. Vasilevskiy, P. B. Demina, E. A. Uskova, B. N. Zvonkov, Appl. Phys. Lett. **2005**, *87*, 053109; h) I. Heckelmann, Z. Lu, J. C. A. Prentice, F. Auras, T. K. Ronson, R. H. Friend, J. R. Nitschke, S. Feldmann, Angew. Chem., Int. Ed. **2023**, *62*, e202216729; i) Z. Chen, C. Dai, W. Xiong, Y. Che, C. Zhang, Commun. Chem. **2021**, *4*, 97; j) J.-D. Zhou, W.-Q. Zhang, L.-L. Liu, Z.-Q. Xie, Y.-G. Ma, Chin. Chem. Lett. **2016**, *27*, 1350; k) X. Zhang, H. Dong, W. Hu, Adv. Mater. **2018**, *30*, e1801048.

[4] a) B. Yin, J. Liang, J. Hao, C. Dai, H. Jia, H. Wang, D. Wang, F.-J. Shu, C. Zhang, J. Gu, Y. S. Zhao, Sci. Adv. **2022**, 8, eabn8106; b) Y. Lv, D. Li, A. Ren, Z. Xiong, Y. Yao, K. Cai, S. Xiang, Z. Zhang, Y. S. Zhao, ACS Appl. Mater. Interfaces **2021**, *13*, 28662; c) I. Hisaki, Y. Suzuki, E. Gomez, Q. Ji, N. Tohnai, T. Nakamura, A. Douhal, J. Am. Chem. Soc. **2019**, *141*, 2111; d) S. Horiuchi, S. Ishibashi, R. Haruki, R. Kumai, S. Inada, S. Aoyagi, Chem. Sci. **2020**, *11*, 6183; e) K. E. Maly, E. Gagnon, T. Maris, J. D. Wuest, J. Am. Chem. Soc. **2007**, *129*, 4306.

[5] X. Song, Y. Wang, C. Wang, D. Wang, G. Zhuang, K. O. Kirlikovali, P. Li, O. K. Farha, J. Am. Chem. Soc. **2022**, *144*, 10663.

[6] a) Y. Shi, S. Wang, W. Tao, J. Guo, S. Xie, Y. Ding, G. Xu, C. Chen, X. Sun, Z. Zhang, Z. He, P. Wei, B. Z. Tang, Nat. Commun. **2022**, *13*, 1882; b) Q. Chen, T. Zhang, X. Chen, M. Liang, H. Zhao, P. Yuan, Y. Han, C.-P. Li, J. Hao, P. Xue, ACS Appl. Mater. Interfaces **2022**, *14*, 24509; c) F. D. J. Brunner, O.-P. Kwon, S.-J. Kwon, M. Jazbinšek, A. Schneider, P. A. Günter, Opt. Express **2008**, *16*, 16496; d) J. Zyss, G. Berthier, J. Chem. Phys. **1982**, *77*, 3635; e) S. Madhankumar, P. Muthuraja, M. Dhandapani, J. Mol. Struct. **2020**, *1203*, 127419; f) Y. C. Yang, X. Liu, X. B. Deng, L. M. Wu, L. Chen, JACS Au **2022**, *2*, 2059; g) J. Zhang, Z. Sun, W. Zhang, C. Ji, S. Liu, S. Han, J. Luo, Cryst. Growth Des. **2017**, *17*, 3250.

[7] a) B. Tang, C. Wang, Y. Wang, H. Zhang, Angew. Chem., Int. Ed. **2017**, *56*, 12543; b) X. Cheng, Z. Wang, B. Tang, H. Zhang, A. Qin, J. Sun, B. Tang, Adv. Funct. Mater. **2018**, *28*, 1706506; c) H.-H. Fang, Q.-D. Chen, J. Yang, H. Xia, B.-R. Gao, J. Feng, Y.-G. Ma, H.-B. Sun, J. Phys. Chem. C **2010**, *114*, 11958; d) Y. Lv, Z. Xiong, Y. Li, D. Li, J. Liang, Y. Yang, F. Xiang, S. Xiang, Y. S. Zhao, Z. Zhang, J. Phys. Chem. Lett. **2022**, *13*, 130; e) B. Tang, S. Tang, C. Qu, K. Ye, Z. Zhang, H. Zhang, CCS Chem. **2023**, *5*, 2348; f) R. Huang, C. Wang, Y. Wang, H. Zhang, Adv. Mater. **2018**, *30*, 1800814; g) G. Zu, S. Li, J. He, H. Zhang, H. Fu, J. Phys. Chem. Lett. **2022**, *13*, 5461.
[8] a) H. Ye, L. Cui, T. Matsushima, C. Qin, C. Adachi, ACS Appl. Mater. Interfaces **2018**, *10*, 27; b) V. T. N. Mai, A. Shukla, M. Mamada, S. Maeder, P. E. Shaw, J. Sobus, I. Allison, C. Adachi, E. B. Namdas, S.-C. Lo, ACS Photonics **2018**, *5*, 4447; c) X. Cheng, K. Wang, S. Huang, H. Zhang, H. Zhang, Y. Wang, Angew. Chem., Int. Ed. **2015**, *54*, 8369; d) Z. Xu, Z. Zhang, X. Jin, Q. Liao, H. Fu, Chem. Asian J. **2017**, *12*, 2985; e) S.-B. Ruan, C.-Y. Chan, H. Ye, K. Inada, F. Bencheikh, A. S. D. Sandanayaka, T. Matsushima, C. Adachi, Opt. Mater. **2020**, *100*, 109636; f) N. M. Hoinka, T. Fuhrmann-Lieker, Sci. Rep. **2019**, *9*, 1862; g) R. Medishetty, V. Nalla, L. Nemec, S. Henke, D. Mayer, H. Sun, K. Reuter, R. A. Fischer, Adv. Mater. **2017**, *29*, 1605637; h) H. Liu, Z. Lu, B. Tang, Z. Zhang, Y. Wang, H. Zhang, Dyes Pigm. **2018**, *149*, 284.

[9] a) Q. Liao, X. Jin, H. Zhang, Z. Xu, J. Yao, H. Fu, Angew. Chem., Int. Ed. **2015**, *54*, 7037; b) H. Mizuno, U. Haku, Y. Marutani, A. Ishizumi, H. Yanagi, F. Sasaki, S. Hotta, Adv. Mater. **2012**, *24*, 5744; c) Z. Xu, Q. Liao, Q. Shi, H. Zhang, J. Yao, H. Fu, Adv. Mater. **2012**, *24*, OP216; d) J. Feng, W. Wen, X. Wei, X. Jiang, M. Cao, X. Wang, X. Zhang, L. Jiang, Y. Wu, Adv. Mater. **2019**, *31*, 1807880; e) C. Zhang, C.-L. Zou, Y. Zhao, C.-H. Dong, C. Wei, H. Wang, Y. Liu, G.-C. Guo, J. Yao, Y. S. Zhao, Sci. Adv. **2015**, *1*, e1500257; f) M. Liu, H. S. Quah, S. Wen, Y. Li, J. J. Vittal, W. Ji, J. Phys. Chem. C **2018**, *122*, 777; g) K. P. Bera, S. Kamal, A. I. Inamdar, B. Sainbileg, H.-I. Lin, Y.-M. Liao, R. Ghosh, T.-J. Chang, Y.-G. Lee, H. Cheng-Fu, Y.-T. Hsu, M. Hayashi, C.-H. Hung, T.-T. Luo, K.-L. Lu, Y.-F. Chen, ACS Appl. Mater. Interfaces **2020**, *12*, 36485; h) Y. Lv, Z. Xiong, H. Dong, C. Wei, Y. Yang, A. Ren, Z. Yao, Y. Li, S. Xiang, Z. Zhang, Y. S. Zhao, Nano Lett. **2020**, *20*, 2020; i) Y. Lv, Z. Xiong, Y. Yao, A. Ren, S. Xiang, Y. S. Zhao, Z. Zhang, Chem. - Eur. J. **2021**, *27*, 3297; j) H. Dong, C. Zhang, Y. Liu, Y. Yan, F. Hu, Y. S. Zhao, Angew. Chem., Int. Ed. **2018**, *57*, 3108; k) C.-C. Yan, Y.-P. Liu, W.-Y. Yang, J.-J. Wu, X.-D. Wang, L.-S. Liao, Angew. Chem., Int. Ed. **2022**, *61*, e202210422; l) B. Tang, S. Tang, K. Ye, H. Zhang, Org. Mater. **2022**, *4*, 216; m) X. Chu, Z. Lu, B. Tang, B. Liu, K. Ye, H. Zhang, J. Phys. Chem. Lett. **2020**, *11*, 5433; n) X. Li, N. Gao, Y. Xu, F. Li, Y. Ma, Appl. Phys. Lett. **2012**, *101*, 063301; o) S. Kéna-Cohen, S. R. Forrest, Nat. Photonics **2010**, *4*, 371; p) A. V. Zasedatelev, A. V. Baranikov, D. Urbonas, F. Scafirmuto, U. Scherf, T. Stöferle, R. F. Mahrt, P. G. Lagoudakis, Nat. Photonics **2019**, *13*, 378; q) T. Matsuo, Y. Ueda, H. Mizuno, F. Sasaki, K. Yamashita, H. Yanagi, ACS Photonics **2022**, *9*, 2015; r) M. Wei, A. Ruseckas, V. T. N. Mai, A. Shukla, I. Allison, S.-C. Lo, E. B. Namdas, G. A. Turnbull, I. D. W. Samuel, Laser Photonics Rev. **2021**, *15*, 2100028; s) J. Liang, Y. Yan, Y. S. Zhao, Acc. Mater. Res. **2021**, *2*, 340; t) A. J. C. Kuehne, M. C. Gather, Chem. Rev. **2016**, *116*, 12823.

[10] a) L. Chen, P.-Y. Fu, H.-P. Wang, M. Pan, Adv. Opt. Mater. **2021**, *9*, 2001952; b) C. E. Small, S. Chen, J. Subbiah, C. M. Amb, S.-W. Tsang, T.-H. Lai, J. R. Reynolds, F. So, Nat. Photonics **2012**, *6*, 115; c) H. Bohra, M. Wang, J. Mater. Chem. A **2017**, *5*, 11550; d) E. Gunina, M. Timofeeva, Y. A. Kenzhebayeva, S. Bachinin, I. A. Gorbunova, D. A. Shipilovskikh, V. A. Milichko, S. A. Shipilovskikh, Photonics Nanostruct. – Fund. Appl. **2023**, *56*, 101168; e) D. Çakal, S. Ertan, A. Cihaner, A. M. Önal, Dyes Pigm. **2018**, *158*, 175; f) E. Gunina, N. Zhestkij, S. Bachinin, S. P. Fisenko, D. A. Shipilovskikh, V. A. Milichko, S. A. Shipilovskikh, Photonics Nanostruct. – Fund. Appl. **2022**, *48*, 100990; g) P. Berrouard, S. Dufresne, A. Pron, J. Veilleux, M. Leclerc, J. Org. Chem. **2012**, *77*, 8167; h) A. Rogova, I. A. Gorbunova, T. E. Karpov, R. Y. Sidorov, A. E. Rubtsov, D. A. Shipilovskikh, A. R. Muslimov, M. V. Zyuzin, A. S. Timin, S. A. Shipilovskikh, J. Med. Chem. **2023**, *254*, 115325; i) W. Wang, J. He, J. Yang, C. Zhang, Z. Cheng, Y. Zhang, Q. Zhang, P. Wang, S. Tang, X. Wang, M. Liu, W. Lu, H.-K. Zhang, J. Med. Chem. **2022**, *65*, 7896.

[11] a) S. J. Lim, M. U. Zahid, P. Le, L. Ma, D. Entenberg, A. S. Harney, J. Condeelis, A. M. Smith, Nat. Commun. **2015**, *6*, 8210; b) Z. Jiang, M. J. Krysmann, A. Kelarakis, P. Koutnik, P. Anzenbacher, P. J. Roland, R. Ellingson, L. Sun, MRS Adv. **2017**, *2*, 2927; c) B. Dong, L. M. Almassalha, Y. Stypula-Cyrus, B. E. Urban, J. E. Chandler, T.-Q. Nguyen, C. Sun, H. F. Zhang, V. Backman, Proc. Natl. Acad. Sci. USA **2016**, *113*, 9716.