Anion Template Research Articles

Epitaxial Growth of Silver Clusters from Ag57 to Ag72 via Laminating Multiple Different Anion Templates.

The established capability of anion templates in precisely manipulating the size, geometry, and function of metal clusters is well acknowledged. However, the development of a systematic methodology for orchestrating the assembly of silver clusters, particularly those encompassing multiple distinct types of anion templates, remains elusive due to the formidable synthetic challenge. In this work, we report two novel silver clusters, Ag57 and Ag72, using two and three different anion templates, respectively. Ag57 features a gyroscope-like monovalent cation with an Ag3 triangle core sandwiched by one [SiW9O34]10- and a triad of Cl- anion templates. By intentionally introducing the third anion template, SO42-, the structure is expanded to the unprecedented Ag72 (with 15 silver atoms epitaxially grown on top of Ag57) resembling a tumbler, inside of which two Ag3 layers are laminated by one [SiW9O34]10-, seven Cl- and one SO42- anion templates in parallel with respect to longitudinal orientation. It is noteworthy that Ag72 exhibits remarkable structural complexity and represents a pioneering achievement as the first silver cluster incorporating three distinct types of anion templates. In addition, Ag72 demonstrates a significant advantage over Ag57, particular in terms of applications such as luminescent thermometers and remote laser ignition.

Epitaxial Growth of Silver Clusters from Ag57 to Ag72 via Laminating Multiple Different Anion Templates

The established capability of anion templates in precisely manipulating the size, geometry, and function of metal clusters is well acknowledged. However, the development of a systematic methodology for orchestrating the assembly of silver clusters, particularly those encompassing multiple distinct types of anion templates, remains elusive due to the formidable synthetic challenge. In this work, we report two novel silver clusters, Ag57 and Ag72, using two and three different anion templates, respectively. Ag57 features a gyroscope‐like monovalent cation with an Ag3 triangle core sandwiched by one [SiW9O34]10− and a triad of Cl− anion templates. By intentionally introducing the third anion template, SO42−, the structure is expanded to the unprecedented Ag72 (with 15 silver atoms epitaxially grown on top of Ag57) resembling a tumbler, inside of which two Ag3 layers are laminated by one [SiW9O34]10−, seven Cl− and one SO42− anion templates in parallel with respect to longitudinal orientation. It is noteworthy that Ag72 exhibits remarkable structural complexity and represents a pioneering achievement as the first silver cluster incorporating three distinct types of anion templates. In addition, Ag72 demonstrates a significant advantage over Ag57, particular in terms of applications such as luminescent thermometers and remote laser ignition.

Synthesis and evaluation of a novel ternary quaternary ammonium salts-fluorescent template copolymer: Integrating flocculation, sterilization, and monitoring functions

Developing flocculants with sterilization and monitoring functions is of practical significance for optimizing water treatment agents. In this research, a fluorescent monomer, EtFl, with double bonds was synthesized and copolymerized with acrylamide (AM) and 3-(methacryloyloxy)propyltrimethylammonium chloride (MAPTAC) using a linear anionic template agent. This synthesis successfully produced a multifunctional template copolymer, TP(AM-MAP-EtFl), with flocculation, sterilization and monitoring capabilities. The fluorescence intensity of TP(AM-MAP-EtFl) was measured using a fluorescence spectrophotometer, demonstrating strong performance even with an EtFl monomer mass fraction as low as 0.5 wt‰, resulting in a fluorescence intensity value of 1000 a.u., suitable for analytical detection. In flocculation experiments with simulated wastewater containing E. coli, the introduction of the fluorescent monomer did not affect E. coli flocculation. When flocculation conditions are optimized, the OD600 readings of the clear liquid remaining after treating with TP(AM-MAP-EtFl#0.5) and TP(AM-MAP-EtFl#5) are 0.0297 and 0.0457, respectively, illustrating superior sterilization effects. Interestingly, SEM and 3D-EEM results confirmed TP(AM-MAP-EtFl)’s bactericidal effect on E. coli, with the introduction of the fluorescent monomer not affecting the sterilization capability of quaternary ammonium. This work integrates flocculation, sterilization and fluorescence properties to provide sterilization-type flocculants with monitoring capabilities, enabling accurate calculation of polymer concentration by detecting solution fluorescence intensity, thereby offering potential for online detection and automatic control of water treatment systems, demonstrating good applicability.

Multi-Template-Guided Synthesis of High-Dimensional Molecular Assemblies for Humidity Gradient-Based Power Generators.

Systematically orchestrating fundamental building blocks into intricate high-dimensional molecular assemblies at molecular level is imperative for multifunctionality integration. However, this remains a formidable task in crystal engineering due to the dynamic nature of inorganic building blocks. Herein, we develop a multi-template-guided strategy to control building blocks. The coordination modes of ligands and the spatial hindrance of anionic templates are pivotal in dictating the overall structures. Flexible multi-dentate linkers selectively promote the formation of oligomeric assembly ([TeO3(Mo2O2S2)3O2(OH)(C5O2H7)3]4- {TeMo6}) into tetrahedral cages ([(TeO3)4(Mo2O2S2)12(OH)12(C9H9O4P)6]8- {Te4Mo24} and [(AsO4)4(Mo2O2S2)12(OH)12(C9H9O6)4]12- {As4Mo24}), while steric hindrance from anionic templates further assists in assembling cages into an open quadruply twisted Möbius nanobelt ([(C6H5O3P)8(Mo2O2S2)24(OH)24(C8H10O4)12]16- {P8Mo48}). Among these structures, the hydrophilic-hydrophobic hybrid cage {Te4Mo24} emerges as an exemplary molecular model for proton conduction and serves as a prototype for humidity gradient-based power generators (HGPGs). The Te4Mo24-PVDF-based HGPG (PVDF=Poly(vinylidene fluoride)) exhibits notable stability and power generation, yielding an open-circuit voltage of 0.51 V and a current density of 77.8 nA cm-2 at room temperature and 90 % relative humidity (RH). Further insights into the interactions between water molecules and microscale molecules within the generator are achieved through molecular dynamics simulations. This endeavor unveils a universal strategy for synthesizing multifunctional integration molecules.

Multi‐Template‐Guided Synthesis of High‐Dimensional Molecular Assemblies for Humidity Gradient‐Based Power Generators

Systematically orchestrating fundamental building blocks into intricate high‐dimensional molecular assemblies at molecular level is imperative for multifunctionality integration. However, this remains a formidable task in crystal engineering due to the dynamic nature of inorganic building blocks. Herein, we develop a multi‐template‐guided strategy to control building blocks. The coordination modes of ligands and the spatial hindrance of anionic templates are pivotal in dictating the overall structures. Flexible multi‐dentate linkers selectively promote the formation of oligomeric assembly ([TeO3(Mo2O2S2)3O2(OH)(C5O2H7)3]4‐ {TeMo6}) into tetrahedral cages ([(TeO3)4(Mo2O2S2)12(OH)12(C9H9O4P)6]8‐ {Te4Mo24} and [(AsO4)4(Mo2O2S2)12(OH)12(C9H9O6)4]12‐ {As4Mo24}), while steric hindrance from anionic templates further assists in assembling cages into an open quadruply twisted Möbius nanobelt ([(C6H5O3P)8(Mo2O2S2)24(OH)24(C8H10O4)12]16‐ {P8Mo48}). Among these structures, the hydrophilic‐hydrophobic hybrid cage {Te4Mo24} emerges as an exemplary molecular model for proton conduction and serves as a prototype for humidity gradient‐based power generators (HGPGs). The Te4Mo24‐PVDF‐based HGPG (PVDF = Poly(vinylidene fluoride)) exhibits notable stability and power generation, yielding an open‐circuit voltage of 0.51 V and a current density of 77.8 nA cm‐2 at room temperature and 90% relative humidity (RH). Further insights into the interactions between water molecules and microscale molecules within the generator are achieved through molecular dynamics simulations. This endeavor unveils a universal strategy for synthesizing multifunctional integration molecules.

Enantiopure trigonal bipyramidal coordination cages templated by in situ self-organized D2h-symmetric anions

The control of a molecule’s geometry, chirality, and physical properties has long been a challenging pursuit. Our study introduces a dependable method for assembling D3-symmetric trigonal bipyramidal coordination cages. Specifically, D2h-symmetric anions, like oxalate and chloranilic anions, self-organize around a metal ion to form chiral-at-metal anionic complexes, which template the formation of D3-symmetric trigonal bipyramidal coordination cages. The chirality of the trigonal bipyramid is determined by the point chirality of chiral amines used in forming the ligands. Additionally, these cages exhibit chiral selectivity for the included chiral-at-metal anionic template. Our method is broadly applicable to various ligand systems, enabling the construction of larger cages when larger D2h-symmetric anions, like chloranilic anions, are employed. Furthermore, we successfully produce enantiopure trigonal bipyramidal cages with anthracene-containing backbones using this approach, which would be otherwise infeasible. These cages exhibit circularly polarized luminescence, which is modulable through the reversible photo-oxygenation of the anthracenes.

Anion Modulation of Ag-Imidazole Cuboctahedral Cage Microenvironments for Efficient Electrocatalytic CO2 Reduction.

How to achieve CO2 electroreduction in high efficiency is a current challenge with the mechanism not well understood yet. The metal-organic cages with multiple metal sites, tunable active centers, and well-defined microenvironments may provide a promising catalyst model. Here, we report self-assembly of Ag4L4 type cuboctahedral cages from coordination dynamic Ag+ ion and triangular imidazolyl ligand 1,3,5-tris(1-benzylbenzimidazol-2-yl) benzene (Ag-MOC-X, X=NO3, ClO4, BF4) via anion template effect. Notably, Ag-MOC-NO3 achieves the highest CO faradaic efficiency in pH-universal electrolytes of 86.1 % (acidic), 94.1 % (neutral) and 95.3 % (alkaline), much higher than those of Ag-MOC-ClO4 and Ag-MOC-BF4 with just different counter anions. In situ attenuated total reflection Fourier transform infrared spectroscopy observes formation of vital intermediate *COOH for CO2-to-CO conversion. The density functional theory calculations suggest that the adsorption of CO2 on unsaturated Ag-site is stabilized by C-H⋅⋅⋅O hydrogen-bonding of CO2 in a microenvironment surrounded by three benzimidazole rings, and the activation of CO2 is dependent on the coordination dynamics of Ag-centers modulated by the hosted anions through Ag⋅⋅⋅X interactions. This work offers a supramolecular electrocatalytic strategy based on Ag-coordination geometry and host-guest interaction regulation of MOCs as high-efficient electrocatalysts for CO2 reduction to CO which is a key intermediate in chemical industry process.

Anion Modulation of Ag‐Imidazole Cuboctahedral Cage Microenvironments for Efficient Electrocatalytic CO2 Reduction

AbstractHow to achieve CO2 electroreduction in high efficiency is a current challenge with the mechanism not well understood yet. The metal‐organic cages with multiple metal sites, tunable active centers, and well‐defined microenvironments may provide a promising catalyst model. Here, we report self‐assembly of Ag4L4 type cuboctahedral cages from coordination dynamic Ag+ ion and triangular imidazolyl ligand 1,3,5‐tris(1‐benzylbenzimidazol‐2‐yl) benzene (Ag‐MOC‐X, X=NO3, ClO4, BF4) via anion template effect. Notably, Ag‐MOC‐NO3 achieves the highest CO faradaic efficiency in pH‐universal electrolytes of 86.1 % (acidic), 94.1 % (neutral) and 95.3 % (alkaline), much higher than those of Ag‐MOC‐ClO4 and Ag‐MOC‐BF4 with just different counter anions. In situ attenuated total reflection Fourier transform infrared spectroscopy observes formation of vital intermediate *COOH for CO2‐to‐CO conversion. The density functional theory calculations suggest that the adsorption of CO2 on unsaturated Ag‐site is stabilized by C−H⋅⋅⋅O hydrogen‐bonding of CO2 in a microenvironment surrounded by three benzimidazole rings, and the activation of CO2 is dependent on the coordination dynamics of Ag‐centers modulated by the hosted anions through Ag⋅⋅⋅X interactions. This work offers a supramolecular electrocatalytic strategy based on Ag‐coordination geometry and host–guest interaction regulation of MOCs as high‐efficient electrocatalysts for CO2 reduction to CO which is a key intermediate in chemical industry process.

Photocurrent, electrochemical characteristic and photodegradation of two Ag20 cage isomers co-constructed by thiol and carboxylate/sulfonate and induced by CO32– template

Assembly of AgStBu and PhCOOH ligands with the assistance of soluble silver salt CH3COOAg/CF3SO3Ag in methanol, N, N-dimethylformamide (DMF) and dichloromethane solution, yielded two Ag20 cage isomers co-constructed by thiol and carboxylate/sulfonate ligands encapsulating a CO32– anion template, [(CO32–)@Ag20(StBu)10(PhCOO)4(CH3COO)4(DMF)4] (1) and [(CO32–)@Ag20(StBu)10(PhCOO)6(CF3SO3)2(DMF)4]·2DMF (2). The CO32– anion template was generated in situ by fixing atmospheric CO2. The precise structures of 1 and 2 were confirmed by single-crystal X-ray diffractometry (SCXRD). The thermal stability of compounds 1 and 2 was proved by thermogravimetric (TG) analysis, and their solution stability was characterized by nuclear magnetic resonance hydrogen spectroscopy (1H NMR). The absorption spectra, photocurrent responses, and luminescence of compounds 1 and 2 were investigated. In addition, the photodegradation of methylene blue (MB) and cyclic voltammetry characteristic curves of 1 and 2 were also studied.

Two structurally new Lindqvist hexaniobate-templated silver thiolate clusters.

Two structurally new Lindqvist hexaniobate-templated silver thiolate clusters, [Nb6O19@Ag45(iPrS)23(CH3COO)14] (Ag45) and (H3O)4[Nb6O19@Ag41KS2.5O2(H2O)7.5(iPrS)24(CH3COO)5] (Ag41), were synthesized using a facile one-pot solvothermal approach. Single crystal X-ray diffraction analyses revealed the presence of a classical Lindqvist-type [Nb6O19]8- anion template, with iPrS- and CH3COO- surface-protecting ligands in both silver clusters, which can further form two-dimensional Ag45 assembly and one-dimensional Ag41 chain packing structures. Both Ag45 and Ag41 clusters exhibited intriguing photothermal conversion properties and temperature-dependent emission behavior.

Anion-templated synthesis of a switchable fluorescent [2]catenane with sulfate sensing capability.

Anion templation strategies have facilitated the synthesis of various catenane and rotaxane hosts capable of strong and selective binding of anions in competitive solvents. However, this approach has primarily relied on positively charged precursors, limiting the structural diversity and the range of potential applications of the anion-templated mechanically interlocked molecules. Here we demonstrate the synthesis of a rare electroneutral [2]catenane using a powerful, doubly charged sulfate template and a complementary diamidocarbazole-based hydrogen bonding precursor. Owing to the unique three-dimensional hydrogen bonding cavity and the embedded carbazole fluorophores, the resulting catenane receptor functions as a sensitive fluorescent turn-ON sensor for the highly hydrophilic sulfate, even in the presence of a large excess of water. Importantly, the [2]catenane exhibits enhanced binding affinity and selectivity for sulfate over its parent macrocycle and other acyclic diamidocarbazole-based receptors. We demonstrate also, for the first time, that the co-conformation of the catenane may be controlled by reversible acid/base induced protonation and deprotonation of the anionic template, SO42-. This approach pioneers a new strategy to induce molecular motion of interlocked components using switchable anionic templates.

Beyond Anion Template: Polyoxometalate as a Property Influencer in High-Nuclearity Silver Thiolate Cluster.

Two 48-nuclei silver nanocages with similar structures and compositions were synthesized by using Keggin-type polyoxometalates (POMs) BW12 and SiW11Ni as anionic templates. However, their photoluminescence and photocurrent properties showed obvious differences. These results suggest that POMs not only serve as anion templates in constructing silver clusters but also influence their properties.

Ultracycles consisting of macrocycles

Presented here is a one-pot strategy starting from rationally designed macrocyclic precursors for the diverse construction of sophisticated ultracycles. The type and amount of the base were found to significantly influence the macrocyclization outcome. The use of 4.0 equiv. CsF resulted in ultracycles of both types A and B while the presence of CsF larger than 6.0 equiv. produced only type B ultracycles. Existence of anion template increased the total yields and affected the distribution of the ultracycles. The ultracycles can accommodate large organic dicarboxylates anions via multiple anion–π and hydrogen bonds, and show selectivity to the size-matched heptanedioate (C72−). Based on all possible species and relevant equilibrium constants as well as material and charge balances, a numerical iterative algorithm was developed and applied to fit the association constants of B2H with dicarboxylates from glutarate (C52−) to octanedioate (C82−), which gave association constants up to 103 L/mol.

Ionic Liquids-Driven Cluster-to-Cluster Conversion of Polyhydrido Copper(I) Clusters Cu7H5 to Cu8H6 and Cu12H9.

Although ionic liquids (ILs) are of prime interest for the synthesis of various nanomaterials, they are scarcely utilized for the polyhydrido copper(I) [Cu(I)H] clusters. Herein, two air-stable Cu(I)H clusters, [Cu8H6(dppy)6](NTf2)2 (Cu8H6) and {Cu12H9(dppy)6[N(CN)2]3} (Cu12H9), are synthesized in high yields for the first time from the ILs-driven conversion of an unprecedented cluster [Cu7H5(dppy)6](ClO4)2 (Cu7H5) by a facile three-layers diffusion crystal (TLDC) method, strategically introducing IL-NTf2 and IL-N(CN)2 as two types of unusual interfacial crystallized templates, respectively. Their structures are fully characterized by various spectroscopic methods and X-ray crystallography, which shows that the anion of IL plays an important role as an anion template and an anion ligand in controlling the structural conversion of Cu(I)H clusters. Their photophysical properties are also investigated, and it is found that all reported clusters exhibit red luminescence with λem ranging from 600 to 690 nm.

A route to metalloligands consolidated silver nanoclusters by grafting thiacalix[4]arene onto polyoxovanadates

Metalloligands provide a potent strategy for manipulating the surface metal arrangements of metal nanoclusters, but their synthesis and subsequent installation onto metal nanoclusters remains a significant challenge. Herein, two atomically precise silver nanoclusters {Ag14[(TC4A)6(V9O16)](CyS)3} (Ag14) and {Ag43S[(TC4A)2(V4O9)]3(CyS)9(PhCOO)3Cl3(SO4)4(DMF)3·6DMF} (Ag43) are synthesized by controlling reaction temperature (H4TC4A = p-tert-butylthiacalix[4]arene). Interestingly, the 3D scaffold-like [(TC4A)6(V9O16)]11- metalloligand in Ag14 and 1D arcuate [(TC4A)2(V4O9)]6- metalloligand in Ag43 exhibit a dual role that is the internal polyoxovanadates as anion template and the surface TC4A4- as the passivating agent. Furthermore, the thermal-induced structure transformation between Ag14 and Ag43 is achieved based on the temperature-dependent assembly process. Ag14 shows superior photothermal conversion performance than Ag43 in solid state indicating its potential for remote laser ignition. Here, we show the potential of two thiacalix[4]arene modified polyoxovanadates metalloligands in the assembly of metal nanoclusters and provide a cornerstone for the remote laser ignition applications of silver nanoclusters.

Interpenetration Phenomena via Anion Template Effects in Fe(II) and Co(II) Coordination Networks with a Bis-(1,2,4-triazole) Ligand.

Seven new coordination networks, [Fe(tbbt)3](BF4)2 (1), [Co(tbbt)3](BF4)2 (2), [Fe(tbbt)3](ClO4)2 (3), [Co(tbbt)3](ClO4)2 (4), [Fe(NCS)2(tbbt)2] (5), [Co(NCS)2(tbbt)2] (6), and [Fe(H2O)2(tbbt)2]Br2·2H2O (7), were synthesized with the linker 1,1'-(trans-2-butene-1,4-diyl)bis-1,2,4-triazole (tbbt) and structurally investigated. The structure of complexes 1-4 is composed of three interpenetrating, symmetry-related 3D networks. Each individual 3D network forms a primitive, nearly cubic lattice (pcu) with BF4- or ClO4- anions present in the interstitial spaces. The structure of compounds 5 and 6 is composed of two-dimensional sql layers, which are parallel to each other in the AB stacking type. These layers are interpenetrated by one-dimensional chains, both having the same formula unit, [M(NCS)2(tbbt)2] (M = Fe, Co). The structure of compound 7 consists of parallel, two-dimensional sql layers in the ABCD stacking type. The interpenetration in 1-6 is not controlled by π-π-interactions between the triazole rings or C=C bonds, as could have been expected, but by (triazole)C-H⋯F4B, C-H⋯O4Cl, and C-H⋯SCN anion hydrogen bonds, which suggests a template effect of the respective non-coordinated or coordinated anion for the interpenetration. In 7, the (triazole)C-H⋯Br anion interactions are supplemented by O-H⋯O and O-H⋯Br hydrogen bonds involving the aqua ligand and crystal water molecules. It is evident that the coordinated and non-coordinated anions play an essential role in the formation of the networks and guide the interpenetration. All iron(II) coordination networks are colorless, off-white to yellow-orange, and have the metal ions in the high-spin state down to 77 K. Compound 5 stays in the high spin state even at temperatures down to 10 K.

Anionic Templates Drive Conversion between a ZnII9L6 Tricapped Trigonal Prism and ZnII6L4 Pseudo-Octahedra.

This work introduces the use of 8-aminoquinoline subcomponents to generate complex three-dimensional structures. Together with a tris(formylpyridine), 8-aminoquinoline condensed around ZnII templates to produce a tris(tridentate) ligand. This ligand is incorporated into either a tricapped trigonal prismatic ZnII9L6 structure or a pair of pseudo-octahedral ZnII6L4 diastereomers, with S4 and D2 symmetries. Introduction of a methyl group onto the aminoquinoline modulated the coordination sphere of ZnII, which favored the ZnII9L6 structure and disfavored the ZnII6L4 assembly. The tricapped trigonal prismatic ZnII9L6 architecture converted into a single ZnII6L4 cage diastereomer following the addition of a dianionic 4,4'-dinitrostilbene-2,2'-disulfonate guest. Four of these guests clustered tightly at the four windows of the ZnII6L4 cage, held in place through electrostatic interactions and hydrogen bonding, stabilize a single diastereomeric configuration with S4 symmetry.

Anion-induced differential assembly and structural transformation of supramolecular coordination cages

The intimate host-anion interactions will regulate thermodynamics and kinetics in the self-assembly of cationic cages mimicking biological counterparts. Herein, we report construction and transformation of three Pd(II)-based metal-organic cages (MOCs) depending on different anions. Stoichiometric conversions of the lantern-shaped MOC-34 into either octahedral MOC-35 or tricapped trigonal prism MOC-36 are induced by BF4‒ or NO3‒, respectively. MOC-36 is kinetically favored and can undergo quantitative conversion to the thermodynamically preferred MOC-35 upon heating, accelerated by excess BF4‒ to motivate dissociative dynamics of Pd-vertices and lower activation barrier of cage transformation. The guest encapsulation behaviors of MOC-35 and MOC-36 have also been tested. These results manifest a significance of host-anion dynamics beyond complementary anion template, shedding light on the understanding of intricate anion recognition in nature.

Recent progress in dichalcophosphate coinage metal clusters and superatoms.

Atomically precise clusters of group 11 metals (Cu, Ag, and Au) attract considerable attention owing to their remarkable structure and fascinating properties. One of the unique subclasses of these clusters is based on dichalcophosphate ligands of [(RO)2PE2]- type (E = S or Se, and R = alkyl). These ligands successfully stabilise the most diverse Cu, Ag, and Au clusters and superatoms, spanning from simple ones to amazing assemblies featuring unusual structural and bonding patterns. It is noteworthy that such complicated clusters are assembled directly from cheap and simple reagents, metal(I) salts and dichalcophosphate anions. This reaction, when performed in the presence of a hydride or other anion sources, or foreign metal ions, results in hydrido- or anion-templated homo- or heteronuclear structures. In this feature article, we survey the recent advances in this exciting field, highlighting the powerful synthetic capabilities of the system "a metal(I) salt - [(RO)2PX2]- ligands - a templating anion or borohydride" as an inexhaustible platform for the creation of new atomically precise clusters, superatoms, and nanoalloys.

Nectarine Coated with Biopolymeric Nanocapsules Containing Eugenol to Control Brown Rot

Infections in fruits caused by fungi reduce the quantity and quality of food for human consumption, in addition to causing economic losses. In this sense, this study aimed to address the effects of eugenol nanocapsules (NCs) based on chitosan and carboxymethylcellulose in protecting nectarines against Monilinia fructicola, a brown rot agent, a worldwide important disease. NCs were prepared by layer-by-layer (LbL) self-assembly starting from an anionic template and deposition with up to two polymeric layers. The hydrodynamic diameters ranged from 158 nm (nanoemulsion), 360 nm (one polymeric layer) to 398 nm (two polymeric layers). NCs presented, during the in vitro release, the release of eugenol following a first order process. In addition to being in the region of stability (zeta potential ca. |30| mV), the capsules showed good adhesion to the nectarine surface. In relation to brown rot, the eugenol NCs with chitosan proved to be the best formulation compared to nanoemulsion and NCs with two polymeric layers for its control, increasing the probability that the fruits remain without symptoms, even after 7 days. Therefore, this study demonstrated that chitosan NCs containing eugenol could be an alternative to preserve fruit for longer periods in post-harvest.