Graphene Oxide Sheets Decorated with Octahedral Molybdenum Cluster Complexes for Enhanced Photoinactivation of Staphylococcus aureus.

The emergence of multidrug-resistant microbial pathogens poses a significant threat, severely limiting the options for effective antibiotic therapy. This challenge can be overcome through the photoinactivation of pathogenic bacteria using materials generating reactive oxygen species upon exposure to visible light. These species target vital components of living cells, significantly reducing the likelihood of resistance development by the targeted pathogens. In our research, we have developed a nanocomposite material consisting of an aqueous colloidal suspension of graphene oxide sheets adorned with nanoaggregates of octahedral molybdenum cluster complexes. The negative charge of the graphene oxide and the positive charge of the nanoaggregates promoted their electrostatic interaction in aqueous medium and close cohesion between the colloids. Upon illumination with blue light, the colloidal system exerted a potent antibacterial effect against planktonic cultures of Staphylococcus aureus largely surpassing the individual contributions of the components. The underlying mechanism behind this phenomenon lies in the photoinduced electron transfer from the nanoaggregates of the cluster complexes to the graphene oxide sheets, which triggers the generation of reactive oxygen species. Thus, leveraging the unique properties of graphene oxide and light-harvesting octahedral molybdenum cluster complexes can open more effective and resilient antibacterial strategies.

Enhanced NH3 Sensing Performance of Mo Cluster-MoS2 Nanocomposite Thin Films via the Sulfurization of Mo6 Cluster Iodides Precursor.

The high-performance defect-rich MoS2 dominated by sulfur vacancies as well as Mo-rich environments have been extensively studied in many fields, such as nitrogen reduction reactions, hydrogen evolution reactions, as well as sensing devices for NH3, which are attributed to the under-coordinated Mo atoms playing a significant role as catalytic sites in the defect area. In this study, the Mo cluster-MoS2 composite was creatively synthesized through a one-step sulfurization process via H2/H2S gas flow. The Mo6 cluster iodides (MIs) coated on the fluorine-doped tin oxide (FTO) glass substrate via the electrophoretic deposition method (i.e., MI@FTO) were used as a precursor to form a thin-film nanocomposite. Investigations into the structure, reaction mechanism, and NH3 gas sensing performance were carried out in detail. The results indicated that during the gas flowing, the decomposed Mo6 cluster iodides played the role of template and precursor, forming complicated Mo cluster compounds and eventually producing MoS2. These Mo cluster-MoS2 thin-film nanocomposites were fabricated and applied as gas sensors for the first time. It turns out that after the sulfurization process, the response of MI@FTO for NH3 gas increased three times while showing conversion from p-type to n-type semiconductor, which enhances their possibilities for future device applications.

Deep-UV laser direct writing of photoluminescent ZnO submicron patterns: an example of nanoarchitectonics concept.

Micro- and nanopatterning of metal oxide materials is an important process to develop electronic or optoelectronic devices. ZnO is a material of choice for its semiconducting and photoluminescence properties. In the frame of the nanoarchitectonics concept, we have developed and investigated a new process that relies on direct writing laser patterning in the Deep-UV (DUV) range to prepare photoluminescent microstructures of ZnO at room temperature, under air. This process is based on a synthesis of colloidal ZnO nanocrystals (NCs) with a careful choice of the ligands on the surface to obtain an optimal (i) stability of the colloids, (ii) redissolution of the non-insolated parts and (iii) cross-linking of the DUV-insolated parts. The mechanisms of photocrosslinking are studied by different spectroscopic methods. This room temperature process preserves the photoluminescence properties of the NCs and the wavelength used in DUV allows to reach a sub-micrometer resolution, which opens new perspectives for the integration of microstructures on flexible substrates for optoelectronic applications.

A review on functional nanoarchitectonics nanocomposites based on octahedral metal atom clusters (Nb6, Mo6, Ta6, W6, Re6): inorganic 0D and 2D powders and films.

This review is dedicated to various functional nanoarchitectonic nanocomposites based on molecular octahedral metal atom clusters (Nb6, Mo6, Ta6, W6, Re6). Powder and film nanocomposites with two-dimensional, one-dimensional and zero-dimensional morphologies are presented, as well as film matrices from organic polymers to inorganic layered oxides. The high potential and synergetic effects of these nanocomposites for biotechnology applications, photovoltaic, solar control, catalytic, photonic and sensor applications are demonstrated. This review also provides a basic level of understanding how nanocomposites are characterized and processed using different techniques and methods. The main objective of this review would be to provide guiding significance for the design of new high-performance nanocomposites based on transition metal atom clusters.

High performance {Nb5TaX12}@PVP (X = Cl, Br) cluster-based nanocomposites coatings for solar glazing applications.

The development of highly ultraviolet (UV) and near-infrared (NIR) absorbent transparent coatings is an important enabling technology and area of research for environmental sustainability and energy conservation. Different amounts of K4[{Nb5TaXi 12}Xa 6] cluster compounds (X = Cl, Br) dispersed into polyvinylpyrrolidone matrices were prepared by a simple, nontoxic and low-cost wet chemical method. The resulting solutions were used to fabricate visibly transparent, highly UV and NIR absorbent coatings by drop casting. The properties of the solution and films were investigated by complementary techniques (optical absorption, electrospray ionization mass spectrometry and Raman spectroscopy). The UV and NIR absorption of such samples strongly depended on the concentration, dispersion and oxidation state of the [{Nb5TaXi 12}Xa 6] nanocluster-based units. By varying and controlling these parameters, a remarkable improvement of the figures of merit TL/TE and SNIR for solar-glazing applications was achieved compared to the previous results on nanocomposite coatings based on metal atom clusters.

Hafnium Oxide Nanostructured Thin Films: Electrophoretic Deposition Process and DUV Photolithography Patterning.

In the frame of the nanoarchitectonic concept, the objective of this study was to develop simple and easy methods to ensure the preparation of polymorphic HfO2 thin film materials (<200 nm) having the best balance of patterning potential, reproducibility and stability to be used in optical, sensing or electronic fields. The nanostructured HfO2 thin films with micropatterns or continuous morphologies were synthesized by two different methods, i.e., the micropatterning of sol-gel solutions by deep ultraviolet (DUV) photolithography or the electrophoretic deposition (EPD) of HfO2 nanoparticles (HfO2-NPs). Amorphous and monoclinic HfO2 micropatterned nanostructured thin films (HfO2-DUV) were prepared by using a sol-gel solution precursor (HfO2-SG) and spin-coating process following by DUV photolithography, whereas continuous and dense monoclinic HfO2 nanostructured thin films (HfO2-EPD) were prepared by the direct EPD of HfO2-NPs. The HfO2-NPs were prepared by a hydrothermal route and studied through the changing aging temperature, pH and reaction time parameters to produce nanocrystalline particles. Subsequently, based on the colloidal stability study, suspensions of the monoclinic HfO2-NPs with morphologies near spherical, spindle- and rice-like shapes were used to prepare HfO2-EPD thin films on conductive indium-tin oxide-coated glass substrates. Morphology, composition and crystallinity of the HfO2-NPs and thin films were investigated by powder and grazing incidence X-ray diffraction, scanning electron microscopy, transmission electron microscopy and UV-visible spectrophotometry. The EPD and DUV photolithography performances were explored and, in this study, it was clearly demonstrated that these two complementary methods are suitable, simple and effective processes to prepare controllable and tunable HfO2 nanostructures as with homogeneous, dense or micropatterned structures.

Controlling the Deposition Process of Nanoarchitectonic Nanocomposites Based on {Nb6-xTaxXi12}n+ Octahedral Cluster-Based Building Blocks (Xi = Cl, Br; 0 ≤ x ≤ 6, n = 2, 3, 4) for UV-NIR Blockers Coating Applications.

The antagonism between global energy needs and the obligation to slow global warming is a current challenge. In order to ensure sufficient thermal comfort, the automotive, housing and agricultural building sectors are major energy consumers. Solar control materials and more particularly, selective glazing are part of the solutions proposed to reduce global energy consumption and tackle global warming. In this context, these works are focused on developing new highly ultraviolet (UV) and near-infrared (NIR) absorbent nanocomposite coatings based on K4[{Nb6-xTaxXi12}Xa6]. (X = Cl, Br, 0 ≤ x ≤ 6) transition metal cluster compounds. These compounds contain cluster-based active species that are characterized by their strong absorption of UV and NIR radiations as well as their good transparency in the visible range, which makes them particularly attractive for window applications. Their integration, by solution processes, into a silica-polyethylene glycol or polyvinylpyrrolidone matrices is discussed. Of particular interest is the control and the tuning of their optical properties during the integration and shaping processes. The properties of the solutions and films were investigated by complementary techniques (UV-Vis-NIR spectrometry, ESI-MS, SEM, HRTEM, etc.). Results of these works have led to the development of versatile solar control coatings whose optical properties are competitive with commercialized material.

Nanoarchitectonics of Glass Coatings for Near-Infrared Shielding: From Solid-State Cluster-Based Niobium Chlorides to the Shaping of Nanocomposite Films.

The high potential of [{Nb6Cli12}La6] cluster-based building blocks as near-infrared radiation blockers for energy saving applications is exposed in the present paper (i = inner edge-bridging ligand, a = apical ligand of the Nb6; L = H2O and/or Cl). To do so, a combined experimental and theoretical investigation of edge-bridged [{Nb6Cli12}Cla6-x(H2O)x]m+/0/n- cluster unit series (x = 0, 4, 6; m = 2, 3, 4; n = 2, 3, 4) has been carried out. By using the K4[{Nb6Cli12}Cla6] starting solid-state precursor, we explored the behavior of the [{Nb6Cli12}Cla6]4- cluster unit during the different steps of its integration as a building block into a polyvinylpyrrolidone (PVP) matrix to form a glass coating composite denoted {Nb6Cli12}m+@PVP (m = 2 or 3). The optical, vibrational and redox properties [{Nb6Cli12}Cla6-x(H2O)x]m+/0/n- building blocks have been interpreted with the support of electronic structure calculations and simulation of properties. The chemical modifications and oxidation properties have been identified and studied thanks to various techniques in solution. Combining Raman and ultraviolet-visible spectroscopies, electrochemistry, and quantum chemical simulations, we bring new knowledge to the understanding of the evolution of the properties of the [{Nb6Cli12}Cla6-x(H2O)x]m+/0/n- cluster units as a function of the number of valence electron per cluster (VEC) and the nature of terminal ligands (x = 0, n = 4; x = 4, charge = 0; x = 6, m = 4). The fine understanding of the physical properties and vibrational fingerprints depending on the VEC and chemical modifications in solution are mandatory to master the processing of cluster-based building blocks for the controlled design and shaping of glass coating nanocomposites. On the basis of this acquired knowledge, [{Nb6Cli12}Cla6-x(H2O)x]m+/0/n- building blocks were embedded in a PVP matrix. The resulting {Nb6Cli12}2+@PVP nanocomposite film shows excellent ultraviolet (UV, 280-380 nm) and near-infrared (NIR, 780-1080 nm) blocking ability (>90%) and a highly visible light transmittance thanks to the controlled integration of the {Nb6Cli12}2+ cluster core. The figures of merit (FOM) value of Tvis/Tsol (Tvis = visible transmittance and Tsol = solar transmittance) as well as the haze, clarity, and the NIR shielding values (SNIR) were measured. After optimization of the integration process, a {Nb6Cli12}2+@PVP nanocomposite on glass substrate has been obtained with a high FOM equal to 1.29. This high value places the transparent green olive {Nb6Cli12}2+@PVP nanocomposites at the top system in the benchmark in the field of glass coating composites for energy-saving applications.

Surface Plasmon Tunability of Core-Shell Au@Mo6 Nanoparticles by Shell Thickness Modification.

Plasmon resonances of noble metal nanoparticles are used to enhance light-matter interactions in the nanoworld. The nanoparticles' optical response depends strongly on the dielectric permittivity of the surrounding medium. We show that the plasmon resonance energy of core-shell Au@Mo6 nanoparticles can be tuned from 2.4 to 1.6 eV by varying the thickness of their Mo6 cluster shells between zero and 70 nm, when the core diameter is fixed at 100 nm. We probe their plasmonic response by performing nanometer-resolution plasmon mapping on individual nanoparticles, using electron energy-loss spectroscopy inside a transmission electron microscope. Our experimental results are corroborated by numerical simulations performed using boundary element methods. The simulations predict a similar dependency for the extinction energy, showing that this effect could also be observed by light-optical experiments outside the electron microscope, although limited by the size distribution of the nanoparticles in solution and the substantial scattering effects.

Evidence of the Ambipolar Behavior of Mo6 Cluster Iodides in All-Inorganic Solar Cells: A New Example of Nanoarchitectonic Concept.

Ambipolar materials such as carbon nanotubes, graphene, or 2D transition metal chalcogenides are very attractive for a large range of applications, namely, light-emitting transistors, logic circuits, gas sensors, flash memories, and solar cells. In this work, it is shown that the nanoarchitectonics of inorganic Mo6 cluster-based iodides enable to form thin films exhibiting photophysical properties that enable their classification as new members of the restricted family of ambipolar materials. Thus, the electronic properties of the ternary iodide Cs2[{Mo6I8i}I6a] and those of thin films of the aqua-complex-based compound [{Mo6I8i}I4a(H2O)2a]·xH2O were investigated through an in-depth photoelectrochemical study. Once hole/electron pairs are created, the holes and electrons turn to be transported simultaneously in opposite directions, and their lifetimes exhibit similar values. The ambipolar properties were demonstrated via the integration of [{Mo6I8i}I4a(H2O)2a]·xH2O as light harvesters in an all-solid solar cell. A significant photoresponse with a typical diode characteristic clearly provides evidence of the simultaneous transfer and transport of holes and electrons within the [{Mo6I8i}I4a(H2O)2a]·xH2O layer. The ambipolar behavior results, on the one hand, from the confinement of electrons imposed by the nanometric size of the molecular metal clusters and, on the other hand, from the poor electronic interactions between clusters in the solid state. Such molecular structure-based layers lead naturally to an intrinsic semiconducting behavior.

Synthesis of novel hexamolybdenum cluster-functionalized copper hydroxide nanocomposites and its catalytic activity for organic molecule degradation.

A novel heterogeneous catalytic nanomaterial based on a molybdenum cluster-based halide (MC) and a single-layered copper hydroxynitrate (CHN) was first prepared by colloidal processing under ambient conditions. The results of the elemental composition and crystalline pattern indicated that CHN was comprehensively synthesized with the support of the MC compound. The absorbing characteristic in the ultraviolet and near-infrared regions was promoted by both of the ingredients. The proper chemical interaction between the materials is a crucial reason to modify the structure of the MCs and only a small decrease in the magnetic susceptibility of CHN. The heterogeneous catalytic activity of the obtained MC@CHN material was found to have a high efficiency and excellent reuse when it is activated by hydrogen peroxide (H2O2) for the degrading reaction of the organic pollutant at room temperature. A reasonable catalytic mechanism was proposed to explain the distinct role of the copper compound, Mo6 compound, and H2O2 in the production of the radical hydroxyl ion. This novel nanomaterial will be an environmentally promising candidate for dye removal.

Revisiting properties of edge-bridged bromide tantalum clusters in the solid-state, in solution and vice versa: an intertwined experimental and modelling approach.

Edge-bridged halide tantalum clusters based on the {Ta6Br12}4+ core have been the topic of many physicostructural investigations both in solution and in the solid-state. Despite a large number of studies, the fundamental correlations between compositions, local symmetry, electronic structures of [{Ta6Bri12}La6]m+/n- cluster units (L = Br or H2O, in solution and in the solid-state), redox states, and vibrational and absorption properties are still not well established. Using K4[{Ta6Bri12}Bra6] as a starting precursor (i: inner and a: apical), we have investigated the behavior of the [{Ta6Bri12}Bra6]4- cluster unit in terms of oxidation properties and chemical modifications both in solution (water and organic solvent) and after recrystallization. A wide range of experimental techniques in combination with quantum chemical simulations afford new data that allow the puzzling behavior of the cluster units in response to changes in their environment to be revealed. Apical ligands undergo changes like modifications of interatomic distances to complete substitutions in solution that modify noticeably the cluster physical properties. Changes in the oxidation state of the cluster units also occur, which modify significantly their physical properties, including optical properties, which can thus be used as fingerprints. A subtle balance exists between the number of substituted apical ligands and the cluster oxidation state. This study provides new information about the exact nature of the species formed during the transition from the solid-state to solutions and vice versa. This shows new perspectives on optimization protocols for the design of Ta6 cluster-based materials.

Electrophoretically Deposited Layers of Octahedral Molybdenum Cluster Complexes: A Promising Coating for Mitigation of Pathogenic Bacterial Biofilms under Blue Light.

The fight against infective microorganisms is becoming a worldwide priority due to serious concerns about the rising numbers of drug-resistant pathogenic bacteria. In this context, the inactivation of pathogens by singlet oxygen, O2(1Δg), produced by photosensitizers upon light irradiation has become an attractive strategy to combat drug-resistant microbes. To achieve this goal, we electrophoretically deposited O2(1Δg)-photosensitizing octahedral molybdenum cluster complexes on indium-tin oxide-coated glass plates. This procedure led to the first example of molecular photosensitizer layers able to photoinactivate bacterial biofilms. We delineated the morphology, composition, luminescence, and singlet oxygen formation of these layers and correlated these features with their antibacterial activity. Clearly, continuous 460 nm light irradiation imparted the layers with strong antibacterial properties, and the activity of these layers inhibited the biofilm formation and eradicated mature biofilms of Gram-positive Staphylococcus aureus and Enterococcus faecalis, as well as, Gram-negative Pseudomonas aeruginosa and Escherichia coli bacterial strains. Overall, the microstructure-related oxygen diffusivity of the layers and the water stability of the complexes were the most critical parameters for the efficient and durable use. These photoactive layers are attractive for the design of antibacterial surfaces activated by visible light and include additional functionalities such as the conversion of harmful UV/blue light to red light or oxygen sensing.

Zn-Al Layered Double Hydroxide Film Functionalized by a Luminescent Octahedral Molybdenum Cluster: Ultraviolet-Visible Photoconductivity Response.

A novel UV-Vis photodetector consisting of an octahedral molybdenum cluster-functionalized Zn2Al layered double hydroxide (LDH) has been successfully synthesized by co-precipitation and delamination methods under ambient conditions. The electrophoretic deposition process has been used as a low-cost, fast, and effective method to fabricate thin and transparent nanocomposite films containing a dense and regular layered structure. The study provided evidence that the presence of the Mo6 cluster units between the LDH does not affect the ionic conduction mechanism of the LDH, which linearly depends on the relative humidity and temperature. Moreover, the photocurrent response is remarkably extended to the visible domain. The reproducibility and stabilization of the photocurrent response caused by the Mo6 cluster-functionalized LDH have been verified upon light excitation at 540 nm. Additionally, it was demonstrated that the films show advantageously strong adherence properties for application requirements.

Transparent functional nanocomposite films based on octahedral metal clusters: synthesis by electrophoretic deposition process and characterization.

Transparent optical thin films have recently attracted a growing interest for functional window applications. In this study, highly visible transparent nanocomposite films with ultraviolet (UV)-near-infrared (NIR)-blocking capabilities are reported. Such films, composed of Mo6 and Nb6 octahedral metal atom clusters (MC) and polymethylmethacrylate polymer (PMMA), were prepared by electrophoretic deposition on indium tin oxide-coated glass (ITO glass). PMMA was found to improve both the chemical and physical stability of Mo6 and Nb6 MCs, resulting in a relatively homogeneous distribution of the clusters within the PMMA matrix, as seen by microstructural observations. The optical absorption spectrum of these transparent MC@polymer nanocomposite films was marked by contributions from their Mo6 and Nb6-based clusters (absorption in the UV range) and from the ITO layer on silica glass (absorption in the NIR range). Mo6@PMMA nanocomposite films also exhibited excellent photoluminescence properties, which were preserved even after exposure to 50°C at a relative humidity of 70% for one month. These films cumulate high transparency in the visible range with remarkable UV-NIR blocking properties and represent interesting candidates for functional glass application.

ITO@SiO2 and ITO@{M6Br12}@SiO2 (M = Nb, Ta) nanocomposite films for ultraviolet-near infrared shielding.

Transparent optical thin films for energy saving applications have recently gained substantial prominence for functional window processes. In this study, highly visible transparent nanocomposite films with ultraviolet (UV) and near-infrared (NIR) blocking capabilities are reported. Such nanocomposite films, prepared by electrophoretic deposition on ITO-coated glass, are composed of indium tin oxide (ITO) nanocrystals (9 nm) and octahedral metal atom clusters (1 nm, Nb6 or Ta6) embedded into silica nanoparticles (∼80 nm). The functional silica nanoparticles were prepared by a reverse microemulsion process. The microstructural characterization proved that ITO nanocrystals are centered in the silica nanoparticles, whereas the metal atom clusters are homogeneously distributed in the silica matrix. The optical absorption spectra of these transparent nanocomposite films exhibit distinct and complementary contributions from their ITO nanoparticles and metal atom clusters (absorption in the UV range) and from the ITO layer on silica.

The Ouzo effect to selectively assemble molybdenum clusters into nanomarbles or nanocapsules with increased HER activity.

Metal cluster nanoparticles are obtained by simple solvent shifting called the Ouzo effect. Remarkably, the assembly of [{Mo6Br8}L6]2- (L = Br- or NCS-) cluster units can be directed into nanomarbles or nanocapsules depending on the cluster chemistry. When deposited on electrodes, these nanoparticles show good activities in electrochemical water splitting under mild conditions.

Embedding hexanuclear tantalum bromide cluster {Ta6Br12} into SiO2 nanoparticles by reverse microemulsion method.

Hexanuclear tantalum bromide cluster units [{Ta6Bri12}La6] (i = inner, a = apical, L = ligand OH or H2O) are embedded into SiO2 nanoparticles by a reverse microemulsion (RM) based method. [{Ta6Bri12}Bra2 (H2O)a4]·nH2O (noted TBH) and tetraethyl orthosilicate (TEOS) are used as the starting cluster compound and the precursor of SiO2, respectively. The RM system in this study consists of the n-heptane (oil phase), Brij L4 (surfactants), ethanol, TEOS, ammonia solution and TBH aqueous sol. The size and morphology of the product namely {Ta6Br12}@SiO2 nanoparticles are analyzed by HAADF-STEM and EDS mappings. The presence and integrity of {Ta6Br12} in the SiO2 nanoparticles are evidenced by EDS mapping, ICP-OES/IC and XPS analysis. The optical properties of {Ta6Br12}@SiO2 nanoparticles are analyzed by diffuse reflectance UV-vis spectroscopy, further evidencing the integrity of the embedded {Ta6Br12} and revealing their oxidation state. Both {Ta6Br12}2+ and {Ta6Br12}3+ are found in SiO2 nanoparticles, but the latter is much more stable than the former. The by-products in this RM-based synthesis, as well as their related factors, are also discussed.

Evaluation of Functional SiO2 Nanoparticles Toxicity by a 3D Culture Model.

CONTEXT: as a kind of non-metal oxide SiO2 NPs have been extensively used in biomedicine, pharmaceuticals and other industrial manufacturing fields, such as DNA delivery, cancer therapy… Our group had developed a method based on microemulsion process to prepare SiO2 NPs incorporating photonic or magnetic nanocrystals and luminescent nanosized inorganic metal atom clusters. However, the toxicity of nanoparticles is known to be closely related to their physico-chemical characteristics and chemical composition. OBJECT: it is therefore of interest to investigate the toxicity of these novel SiO2 NPs to the cells that may come in contact. MATERIALS AND METHODS: the potential toxic effect of the functional @SiO2 NPs containing Mo6 clusters with or without gold nanoparticles was investigated, at concentrations 1 µg/mL, 10 µg/mL and 100 µg/mL each, on three different cell lines. Cell viability was measured by the MTT test in monolayer's culture whereas the cytotoxicity in spheroid model was examined by the APH assay. In a second time, oxidative-stress-induced cytotoxicity was investigated through glutathione levels dosages. RESULTS: the results indicated that both A549 and L929 cell lines did not exhibit susceptibility to functional @SiO2 NPs-induced oxidative stress unlike KB cells. DISCUSSION: SiO2 NPs containing CMB may become toxic to cultured cells but only at a very high dosage level. Therefore, this toxicity depends on cell lines and more, on the model of cell cultures. The selection of appropriate cell line remains a critical component in nanotoxicology. CONCLUSION: these results are relevant to future applications of SiO2 gold-cluster NPs in controlled release applications.

Electro-click construction of hybrid nanocapsule films with triggered delivery properties.

Hollow nanocapsules (named Hybridosomes®) possessing a polymer/nanoparticle shell were used to covalently construct hybrid films in a one-pot fashion. The alkyne bearing organic/inorganic Hybridosomes® were reticulated with azide bearing homobifunctional polyethyleneglycol (PEG) linkers, by using an electro-click reaction on F-SnO2 (FTO) electrodes. The coatings were obtained by promoting the Cu(i)-catalyzed click reaction between alkyne and azide moieties in the vicinity of the electrode by the electrochemical generation of Cu(i) ions. The physicochemical properties of the covalently reticulated hybrid films obtained were studied by SEM, AFM, UV-vis and fluorescence spectroscopy. The one-pot covalent click reaction between the nanocapsules and the PEG linkers in the film did not affect the desirable features of the Hybridosomes® i.e. their hollow nanostructure their chemical versatility and their pH-sensitivity. Consequently, both the composition and the cargo-loading of the Hybridosomes® films could be tuned, demonstrating the versatility of these hybrid coatings. For example, the Hybridosome® films were used to encapsulate and release a bodipy fluorescent probe in response to either a pH drop or the application of an oxidative +1 V potential (vs. Ag/AgCl) at the substrate. By advancing the field of electro-synthesized films a step further toward the design of complex physicochemical interfaces, these results open perspectives for multifunctional coatings where chemical versatility, controllable stability and a hollow nanostructure are required.