Chemistry - An Asian Journal

Plasmonic materials can be utilized as effective platforms to enhance luminescent signals of luminescent metal nanoclusters (LMNCs). Both surface enhanced fluorescence (SEF) and shell‐isolated nanoparticle‐enhanced fluorescence (SHINEF) strategies take advantage of the localized and increased external electric field created around the plasmonic metal surface when excited at or near their characteristic plasmonic resonance. In this context, we present an experimental and computational study of different plasmonic composites, (Ag) Ag@SiO2 and (Au) Au@SiO2 nanoparticles, which were used to enhance the luminescent signal of Au nanoclusters coated with glutathione (GSH) molecule (Au25GSH NCs). This specific LMNC has recently attracted particular interest due to its luminescent response and characteristic photostability. Our study presents a wide characterization of the optical and morphologic features of the synthetized particles: plasmonic metal nanostructures and Au25GSH NCs through different experimental techniques including UV‐Visible, IR, luminescent spectroscopies, along with TEM and AFM microscopies. Additionally, we have carried out computational simulations based on time‐dependent density functional theory (TD‐DFT) and classical electrodynamics simulation based on Mie Theory to support our experimental findings. In this study, we report up to 3‐fold luminescence enhancement of Au25GSH NCs which is mainly attributed to slow dynamics SEF.

Heavy metal ions are major contributors to water pollution, posing significant threats to both ecological balance and human health due to their carcinogenic properties. The increasing need for heavy metal detection highlights the advantages of electrochemical methods, which offer high sensitivity and efficiency. Herein mesoporous nitrogen containing carbon (MNC) was utilized for the simultaneous determination of heavy metals using square wave voltammetry technique in the established conditions of a buffer pH of 5.0. MNC demonstrated low detection limits (1, 10 and 50 μM), wide linear ranges (1 μM–6 mM, 10 μM–7 mM and 50 μM–17 mM), and high sensitivities (2.5 μA μM⁻¹ cm⁻², 1.03 μA μM⁻¹ cm⁻² and 5.14 mA mM⁻¹ cm⁻²) for, Pb²⁺, Cd²⁺ and Cu²⁺, respectively. Moreover, the reproducibility, and selectivity of the sensor was investigated in the presence of K⁺, Mg²⁺, Zn²⁺, Ni²⁺, and Fe³⁺ which are the possible interferents present in water.

To realize the aim of easy and accurate detection of ammonia and picric acid (PA) in both aqueous and vapor phases based on function‐oriented investigation principles, in the present study, we include a luminescent performance with recognition performance, taking into account the application conditions. Zn(II) ions with luminescence qualities and an amine‐substituted imidazole moiety with selective recognition properties towards picric acid and ammonia are coupled to generate a novel 1D luminous Zn(II) coordination polymer, Zn‐CP [{Zn(II)( 2‐ABZ)2(2‐BDC)}].MeOH]∞, where 2‐ABZ and 2‐BDC stand for terephthalic acid and protonated 2 aminobenzimidazole, respectively. Tests for luminescence recognition demonstrate that Zn‐CP has potent selectivity, and strong sensitivity to ammonia and PA in both media. In both detection processes, the limit of detection (LOD) values are determined to be 40 nm. Spectroscopic and DFT studies reveal that the detection of Trinitrophenol (TNP) primarily involves a synergistic mechanism of Photoinduced Electron Transfer (PET), Fluorescence Resonance Energy Transfer (FRET), and Charge Transfer (CT). In contrast, the detection of ammonia (NH3) vapor is predominantly driven by hydrogen bonding (H‐bonding) formation. The constructed 1D luminous Zn‐CP is a new material that guides the development of novel luminous sensors in the future.

We present a comprehensive account of our efforts directed towards the synthesis of sacubitril, a neprilysin inhibitor used in combination with valsartan and marketed as Entresto™. Our initial approach to the formal synthesis of sacubitril employed a chiral pool strategy, utilizing (S)‐pyroglutamic acid as a key building block and Cu(I)‐mediated Csp²‐Csp³ cross‐coupling as a key transformation. Further investigations led to the development of chiral amine transfer (CAT) reagents‐based stereoselective synthesis. This involved the E‐selective construction of γ‐ylidene‐butenolide from readily available biphenyl bromide and 4‐pentynoic acid, the conversion of this butenolide to its ene‐lactam using chiral amine, and substrate‐controlled diastereoselective reduction of ene‐lactam using Et3SiH or Pd/C, H2 (overall chiral amine transfer) as key transformations. Antipodal lactam intermediates were synthesized using corresponding chiral amines, and the stereochemical outcomes during the ene‐lactam reduction with Et3SiH were rationalized by DFT studies.

The rapid advancement of industrial production has led to an increase in water pollutants, posing a significant threat to public health. With the deepening of research on pollutant adsorbents. The application of silsesquioxane‐based cross‐linked polymer networks in water pollution treatment has gradually attracted people‘s attention. This study introduces two new crosslinked hybrid network, PCS‐OB and PCS‐OP, which were created through one‐step amine‐ene reaction between octa(aminophenyl) silsesquioxane (OAPS) and bismaleimide or N, N′‐1,3‐phenylenedimaleimide. The synthesized hybrid networks were characterized using Fourier‐transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area analysis, thermogravimetric analysis (TGA), and solid‐state nuclear magnetic resonance (NMR) spectroscopy. The successful synthesis of the material is proved. PCS‐OB and PCS‐OP exhibited remarkable efficiency in the adsorption and removal of contaminants such as antibiotics, dyes, and iodine from wastewater. The maximum adsorbents for Rhodamine B (RhB), iodine vapor and berberine hydrochloride (BCH) were 1069 mg g⁻¹, 1590 mg g⁻¹ and 294 mg g⁻¹, respectively. In conclusion, this work proves that PCS‐OB and PCS‐OP have broad application prospects in pollutant treatment.

Visible‐light absorbing metal‐free organic dyes are of increasing demand for various optoelectronic applications because of their great structure‐function tunability through chemical means. Several dyes also show huge potential in triplet photosensitization, generating reactive singlet oxygen. Understanding the structure‐property relationships of many well‐known fluorescein dyes is of paramount importance in designing next‐generation energy efficient dyes, which is currently limited. For example, the role of heavy atoms in the excited‐state deactivations is not fully understood for these dyes. Herein, 9 halogenated (Cl, Br, I) fluorescein dyes with varied halogen concentrations and positions are studied using time‐dependent range‐separated hybrid combined with polarizable continuum model with water dielectric for accounting of polarization and screening effects. Excited state energies of these dyes and their deactivations via radiative and non‐radiative pathways are well described using 0–0 corrected excitation energies. Calculated results are in reasonable agreement with the available experimental data. However, no systematic correlation is found between the heavy‐atom effect and calculated intersystem crossing/fluorescence rates. Not surprisingly, heavy‐atom effect is found to be more pronounced in iodinated dyes compared to their brominated analogues. Halogen position also plays a critical role in determining the excited‐state deactivation rates. All dyes show similar fluorescence rates of ~10⁸ s-1 ${{s}^{-1}}$ . Whereas, the intersystem crossing rates are much smaller and vary from ~10² to 10⁴ s-1 ${{s}^{-1}}$ . Nevertheless, lower fluorescence quantum yields for some dyes are attributed to the large internal conversion. Microscopic understanding on the excited‐state properties of several halogenated fluorescein dyes reported here will aid in developing advanced fluorescein dye based energy efficient photosensitizers and also emitters.

Covalent triazine frameworks, with their ordered pores and crystalline structure that exhibit heteroatom impacts, demonstrate outstanding chemical stability, making them designable for charge storage applications. In this study, the triazine‐based covalent organic frameworks (TPT@BDA‐COF) was synthesized using 4′,4′′′,4′′′′′‐(1,3,5‐Triazine‐2,4,6‐triyl) tris (([1,1′‐biphenyl]‐4‐amine)) (TPT) and 4,4′‐Oxydibenzaldehyde (BDA) following polycondensation process. Interestingly, these resulted in the fabrication of a well‐connected, orderly porous crystalline structure, redox‐active moiety, and significantly high doping atomic percentages of N (~13.6 %). The three‐electrode electrochemical study, showed a stable electrochemical potential window of 1.8 V (−0.45 to +1.35) in 1 M NaClO4 electrolyte, it exhibited a high specific capacitance of 92.6 mF/cm² with a high energy density 41.7 Wh/kg respectively. The symmetric supercapacitor designed using TPT@BDA‐COF as both anode and cathode exhibited high specific capacitance (F/g) and gravimetric energy density (Wh/kg): 17.8, 36.9, 43.7, 47.7 and 3.5, 16.6, 13.7, 21.6 in 1 M CH3COONa, 1 M Na2SO4, 1 M NaNO3, 1 M NaClO4 electrolyte respectively. It showed excellent cyclic stability (105.2 %), and Coulombic efficiency (97.5 %) even after 10 k GCD cycles in 1 M NaClO4 at 2 A/g. Interestingly, ClO4⁻ anions exhibited a better chaotropic nature (water structure breaker) as compared to CH3COO⁻, SO4⁻², and NO3⁻. Their energy storage competence is supported by the illumination of 1 white and 1 red LED upon charging a single SSC for 50 sec each. A Quantum Mechanics (QM) calculation and Molecular Dynamics (MD) simulation are performed to investigate and validate the stability of Covalent Organic Frameworks (COFs). DFT calculations were carried out using the SCF approach B3LYP‐631G(d) basis set to compute the HOMO and LUMO energies and their respective location in COF.

A practical and efficient reaction for C2‐selenylation of 1,4‐naphthoquinones has been explored. This coupling reaction of two redox structural motifs, such as 2‐bromo‐1,4‐naphthoquinone with diaryldiselenide/ebselen has been achieved by using sodium borohydride reducing agent at room temperature. Using this approach, several 2‐selenylated‐1,4‐naphthoquinones were obtained in moderate to good yields and thoroughly characterized by multinuclear (¹H, ¹³C, and ⁷⁷Se) NMR, cyclic voltammetry, and mass spectrometry. Further, light‐irradiated thiolation of the synthesized selenazinone was also performed to show the utility of the synthesized compound for post‐functionalization. Several 2‐selenylated‐1,4‐naphthoquinones were studied by SC‐XRD in which intramolecular Se⋅⋅⋅N (from quinolinyl ligand) non‐bonded interactions were observed. Photophysical studies (UV‐visible, emission, solvatochromism, and quantum yield) were also performed on selected C2‐selenylated naphthoquinones. The naphthoquinonyl organoseleniums were also screened for their antibacterial properties and quinonyl organoselenium 5 d shows good antibacterial potential against S. aureus ATCC 29213 with MIC 0.5 μg/mL and a Selectivity Index of >200. Moreover, it also exhibited equipotent activity against various strains of S. aureus and Enterococcus faecium, including strains resistant to vancomycin and meropenem. From structure‐activity correlation, it seems that nice blend of oxidant properties from quinone and antioxidant properties from selenium moiety makes it better candidate for antibacterial activity.

This article is an editorial about The XXI Brazilian Meeting on Inorganic Chemistry (BMIC). The XXI Brazilian Meeting on Inorganic Chemistry is one of the most important inorganic chemistry events in Latin America. This editorial introduces the event and the papers featured in the special issue celebrating BMIC in Chemistry An Asian Journal. image

In this paper, a new carbon dot (R1‐CDs) was prepared by one‐pot hydrothermal method by using 1,8‐diaminonaphthalene and o‐phthalic acid (o‐PA) as precursors. Due to the high purity of R1‐CDs, NMR analysis was performed to identify the types of H and C atoms in their graphene sheets. From our research findings, three important information was disclosed such as (1) five types H atoms are presented in R1‐CDs; (2) 18 kinds of C atoms in the graphene sheets are observed, and 8 kinds of them are quaternary atoms, and 10 kinds of carbon atoms as tertiary one; (3) functional groups of ‐COOH and ‐NH2 from precursors cannot be inherited into the edges or defect sites of graphene sheet. Obviously, our research findings for the first time revealed the more details of chemical structures of CDs. We believe that our works can supply a general concept to fabricate CDs by selecting specific precursors, also can encourage CDs’ development in a more “chemistry” way by employing NMR as a powerful method.

Using a direct knitting strategy, we successfully prepared a novel heterogeneous catalyst consisting of pyridine‐bridged bis(imidazolium‐2‐ylidene) palladium complexes (CNC‐Pd) embedded in a knitted network polymer. The resulting catalysts (HCP‐CNC‐Pd‐d) exhibited high specific surface areas of 982 m2 g‐1 with microporous and mesoporous structures. The large surface area enhances contact between the substrate and the catalytic center, while the strong chelation between CNC and the metal ion ensures the catalyst's durability. The HCP‐CNC‐Pd‐d catalysts exhibited superior performance, achieving an impressive 99% yield in the Suzuki coupling reaction between bromobenzene and phenylboronic acid. The catalyst also demonstrated good performance across a range of substrates in the Suzuki‐Miyaura coupling reactions. Furthermore, the catalyst could be recycled for over 10 cycles without any significant loss in activity and selectivity. This highly cost‐effective and convenient approach provides valuable insights into the design and application of heterogeneous catalysts in various fields.

The control of the sequential self‐assembly processes of highly entangled (Ag3L2)n (n=2,4,6,8) and Ag21L12 coordination polyhedra using side‐chain effects was studied via the introduction of linear or branched side chains into the tripodal ligands. In addition to changes in the intermediate polyhedral species affording the multi‐ pathway process, disruption of the kinetic control of the sequential self‐assembly was observed, thus demonstrating the utility of steric control for the construction of 3D‐entangled molecular materials on the 5 nm scale with high molecular complexity.

Advanced porous nanomaterials have recently been the subject of considerable interest due to their high surface areas, tunable pore structures, high porosity, and ease of modification. In the chemiluminescence (CL) domain, the incorporation of additional pores into nanostructures not only enhances the loading capacity for signal amplification but also allows the confinement effect in a nanoscale microreactor and the controlled release of reaction agents. In light of this, increasing efforts have been made to fabricate various porous nanomaterials and explore their potential applications in CL assays. This review therefore aims to highlight the recent advances in preparation strategies and basic attributes of the CL‐related porous nanomaterials. Moreover, it offers a comprehensive summary of the emerging CL sensing applications based on these materials. The key challenges and future perspectives of porous nanomaterials in CL assays are finally discussed.

This article is an editorial about the XIX Brazilian Meeting on Organic Synthesis (BMOS). The XIX Brazilian Meeting on Organic Synthesis is one of the most important organic chemistry meetings in Latin America. This editorial introduces the event and the papers featured in the special issue celebrating BMOS in Chemistry An Asian Journal. image

Herein, we describe a sustainable Co(II)‐catalyzed synthesis of pyrroles and pyridines. Using a Co(II)‐catalyst [CoII2(La)2Cl2] (1 a) bearing redox‐active 2‐(phenyldiazenyl)‐1,10‐phenanthroline) (La) scaffold, various substituted pyrroles and pyridines were synthesized in good yields, taking alcohol as one of the primary feedstock. Pyrroles were synthesized by the equimolar reaction of 2‐amino and secondary alcohols. A series of 2,4,6‐substituted symmetrical pyridines were prepared via a three‐component reaction of NH4OAc with 1 : 2.2 molar primary and secondary alcohols, respectively. Unsymmetrically substituted 2,4,6‐trisubstituted, 2,4,5,6‐tetrasubstituted, and 2,3,4,5,6‐pentasubstituted pyridines were achieved via a multi‐component coupling reaction of alcohols and NH4OAc. Catalyst 1 a showed encouraging results during the gram‐scale synthesis of these N‐heterocycles. Mechanistic investigation revealed synergistic involvement of cobalt metal and the ligand during the catalytic reactions.

The reverse water gas shift (RWGS) reaction provides a convenient approach to convert CO2 to CO, which facilitates to achieve the goals of carbon peaking and carbon neutrality. Herein, the Cu/CeO2 catalyst prepared by a co‐precipitation method using a mixture of Na2CO3 and NaOH at pH of 10 (sample Cu/CeO2‐10) achieved an intrinsic reaction rate of 428.4 mmol ⋅ gcat⁻¹ ⋅ h⁻¹ with 100 % CO selectivity at 400 °C and CO2/H2 ratio of 1 : 4, which is much higher than Cu/CeO2 prepared by impregnation and other methods. Various characterizations showed the highest fraction of CuCeO2 solid solution in the calcined Cu/CeO2‐10, and formed highly dispersed Cu clusters (~2.5 nm) on partially reduced CuCeO2 solid solution with abundant of oxygen vacancies upon reduction. The Cu and oxygen vacancies facilitates the activation of H2 and CO2, respectively, resulting in lowered H2 and CO2 reaction orders. As a result, the synergy between the two components enhanced the overall RWGS activity with lowered activation energy. Moreover, the optimal catalyst is very stable in 24 h stability test without detectable agglomeration of Cu clusters.

In this study, we present a protecting group photocleavage method to investigate both covalent and noncovalent interactions between a squaraine dye (PSq) and Bovine Serum Albumin (BSA). This approach allows for the photoinduced activation and deactivation of PSq fluorescence, providing valuable insights into the dual‐mode interaction of the dye with the protein.

Regioselective C−H difluoroalkylation of diverse 2‐pyridones with ethyl bromodifluoroacetates and bromodifluoroacetamides is accomplished by using a (dppf)NiCl2 catalyst under mild conditions. This efficient protocol could deliver a variety of C‐3 difluoroalkylated pyridones with the tolerance of a range of highly susceptible functionalities, such as −Cl, −Br, −I, −COMe, −CN, −NMe2 and −NO2, including heteroarenes like pyridinyl, furanyl, thiophenyl and carbazolyl moieties. A preliminary mechanistic study suggests the radical pathway for the reaction involving fluoroalkyl radical intermediate.

It is required to have a more straightforward and easier way to check the quality of food to ensure the safety of the public heaths. The decomposition of meat protein results in ammonia and biogenic amines (BAs). Here, we have designed and synthesized three luminescent‐based probe molecules, which originated from 2‐(2‐hydroxyphenyl) benzothiazole (HBT) derivatives and showed the excited state‐induced proton transfer (ESIPT) phenomenon. The two substituents (OMe and NO2) were used rationally at the para position of HBT, and the electronic properties were evaluated using Hammett substituent constants. The proton donating ability of the O‐H to the acceptor is largely facilitated by the presence of a strong electron‐withdrawing group, which in this case is NO2. The proton transfer rate can be controlled, and in this case, to a slower rate with the influence of the electron donating group OMe. The controllability of proton transfer led us to use it in pH sensing. A prominent and multi‐color change with pH variation was observed in the case of the OMe substituted compound. These probes were further employed for amine sensing, and in addition, strip‐based detection of spoilage of chicken meat was studied for real‐world applications via both contact and non‐contact modes.

For the development of new functional materials for various applications, such as drug or gene delivery and environmental remediation, the relationship between function and morphology has been considered an important aspect for controlling affinity to the targets. However, there are only a few reports on this relationship because the molecular strategy for the precise control of vesicle shape has been restricted. Herein, we report the photocontrol of vesicle shape using azobenzene‐containing amphiphilic switches. The addition of the photoswitches to vesicles composed of phospholipids yielded non‐spherical vesicles. They exhibited reversible deformation between a non‐spherical and spherical shape in response to ultraviolet and visible light illumination, respectively. From the results of the 1H NMR analyses, fluorescence spectra of the environmentally responsive probes, and Π‐A isotherm measurements, the reversible photoresponsivity can be attributed to the changes in the vesicular membrane structures caused by migration of the photoswitches between the aqueous phase and membrane through their photoisomerization.

Organic light‐emitting diodes (OLEDs) has been attracting much extensive interest owing to their advantages of high‐definition and flexible displays. Many advances have been focused on boosting the efficiency and stability. Two innovative dimethylacridine‐based emitters,1,1,2,2‐tetrakis(4‐ (2,7‐di‐tert‐butyl‐9,9‐dimethylacridin‐10(9H)‐yl)phenyl ethene (AcTPE), and bis(4‐(2,7‐di‐tert‐butyl‐9,9‐dimethylacridin‐10(9H)‐yl)phenyl)methanone (Ac2BP) were designed and synthesized, in which TPE‐baesed AcTPE presents AIE properties, and with the phenyl as spacer between the DMAC and carbony, aryl‐ketone‐based Ac2BP doesn’t show AIE properties due to the absence of restriction of intramolecular rotations. As the electron‐withdrawing ability of carbonyl, well‐matched energy levels of the Ac2BP improve carriers transfer and hole injecting process in devices, resulting an efficient green emission with a maximum PE of of 5.64 lm W‐1, a EQE of 10.56% and a maximum CE of 18.27 cd A‐1. They are much higher than that of AcTPE‐based devices (3.45 cd A‐1, 1.18 lm W‐1, and 1.46%). This study provides a promising design strategy for efficient OLED emitters of aryl‐ketone‐architecture.

Bimetallic catalysts have gained attention as promising contenders, owing to the synergistic interaction between two distinct metal centers. In this study, we present two N‐heterocyclic carbene iridium(III) pentamethylcyclopentadienyl complexes [Cp*Ir(fcpyNHC)Cl]PF6 (1) and [Cp*Ir(pyNHC)Cl]PF6 (2) where 1 includes a ferrocene moiety making it a bimetallic complex. Using ceric ammonium nitrate as a sacrificial oxidant, both complexes were tested for water oxidation. Complex 2 achieved a maximum turnover number (TONmax) of 3240 and a turnover frequency (TOFmax) of 231 min⁻¹. In comparison, complex 1 demonstrated nearly double the activity with a TONmax of 6047 and TOFmax of 431 min⁻¹ compared to 2, which was attributed to the cooperative effect of the catalyst in water oxidation reaction. This bimetallic Fe Ir catalyst (1) exhibited outstanding catalytic efficiency for oxygen evolution from water at ambient conditions. We identified a proposed FeIII IrIV intermediate experimentally via UV‐Vis spectroscopy and XPS study. Theoretically, this intermediate was more stable by 7.84 kcal/mol than the traditional FeII IrV electromer intermediate. This delineates the pronounced bimetallic cooperative participation of both Fe and Ir metal centres for better activity.

The crystallization of lanthanide‐containing β‐octamolybdate (β‐{Mo8O26}⁴⁻) based solids from a binary 1 : 1 (water/DMSO) solution under ambient conditions is reported. A uniform synthetic protocol yielded three structurally related series of general composition {Ln(solvent)n}[NaMo8O26] ⋅ yH2O, with the whole lanthanide series (except for radioactive Pm). The three series are (i) {Ln(DMSO)8}[NaMo8O26] ⋅ 0.5H2O, Ln=La, Ce, Pr, Nd and Sm (Series C1); (ii) {Ln(DMSO)6(H2O)2}[NaMo8O26] for Ln=Eu, Gd, Tb, Dy and Ho (Series C2) and (iii) [{Ln(DMSO)7}][NaMo8O26] ⋅ H2O for Ln=Dy, Ho, Er, Tm, Yb and Lu (Series C3). All solids reported here contain [−β‐Mo8O26−Na−β‐Mo8O26−] anionic chains, which is the dominant feature in the crystal packing of these solids. The chains interacted via hydrogen bonds with the solvated lanthanide counter cations. Lanthanide contraction brings about the difference in the primary coordination sphere of the Ln³⁺ cations in the three series reported here. This manifests in the crystal structure as a change in the relative orientation of chains (or clusters) and the position of Ln³⁺ centers, with water acting as the structure director. The study demonstrates Nature's parsimonious ability to optimize intermolecular interactions via diminutive deviations from recognizable packing patterns when a crystal nucleates from solution.

Investigating solid‐state photoreactivity, driven by crystal packing, has been a major enduring research theme in Crystal Engineering. Trans‐3‐styryl pyridine (3‐StPy), an unsymmetric olefin, is photo‐stable. However, when converted to a series of salts, they exhibited solid‐state photoreactivity under UV irradiation. Crystal structures of 3‐StPy, its protonated salts, namely, (3‐StPyH)(HSO4) ⋅ H2O (1), (3‐StPyH)(CF3CO2) (2), and (3‐StPyH)(p‐Tol‐SO3) (3), and methylated salt (3‐StPyMe)I (4) were determined by X‐ray diffraction. 3‐StPy molecules were found not to align in the parallel arrangement required to undergo solid‐state [2+2] photocycloaddition reaction; however, upon protonation and methylation, the unsymmetric 3‐StPyH⁺ and [3‐StPyMe]⁺ cations aligned in a head‐to‐tail parallel arrangement, predominantly governed by the cation⋅⋅⋅π interactions. Various structural features, e. g., the patterns of hydrogen bonding, etc. have been addressed, and established by Hirshfeld surface analysis. The salt with p‐tolyl sulfonate anion (3) with Z′>1 represents a rare crystal class. It was also noted that the crystals of 1 and 2 melted into a liquid state upon photodimerization reaction. UV‐vis absorption and fluorescence properties have been explored. The electronic structures of 3‐StPy, 3‐StPyH⁺, [3‐StPyMe]⁺, and the dimer [3,3′‐MPyPhCB]²⁺ cations have been elucidated by DFT calculations, and the effect of N‐quaternization on crystal structures and photophysical properties has been discussed.

Gold nanoclusters (AuNCs), which are approximately 2 nm in size, exhibit distinctive photophysical and catalytic properties, but their performance is often compromised by environmental factors. To mitigate these challenges, attempts have been made to incorporate AuNCs into polymer matrices to enhance their stability. Miniemulsion polymerization has proven to be an effective method for fabricating organic‐inorganic composites. Here, we present a facile photothermal‐assisted method for miniemulsion polymerization utilizing AuNCs, which serve as co‐stabilizers of the emulsion and photothermal conversion agents. By grafting tryptamine onto hydrophilic AuNCs, the amphiphilic AuNCs were spontaneously adsorbed at the styrene/water interfaces, resulting in stable nanoemulsions. Taking advantage of the photothermal properties of surface‐bounded AuNCs, rapid polymerization of styrene within the nanoemulsion was successfully initiated by external laser irradiation. The prepared nanocomposites inherited the photothermal activity of AuNCs and exhibited good photothermal stability and repeatability. This approach not only facilitates remote control of chemical reactions, but also optimizes the distribution of AuNCs within the final polymer matrix, thereby enabling the efficient synthesis of nanocomposites while exploiting the unique photofunctionality of AuNCs.