Unraveling the Origin of Unusual Cs Atom Disorder in Cesium Octahedral Molybdenum Halide Cluster Compounds, Cs[{MoX}X] (X = Cl and Br).

In this study, we investigate structural disorder and its implications in metal cluster (MC)-based compounds, specifically focusing on Cs[{MoX}X] (X = Cl and Br). Utilizing synchrotron radiation X-ray diffraction, Fourier transform infrared spectroscopy, and luminescence measurements, we examined the incorporation of water molecules into these compounds and their effects on the crystal structure and optical properties. Our findings reveal that the presence of water molecules induces the lattice disorder, particularly the displacement of Cs atoms.

Emissive supramolecular ionic crystals combining a red-NIR phosphorescent [ReSeCN] cluster anion and a blue fluorescent tetraphenylethene counter-cation.

A blue fluorescent tetraphenylethylene-based dication and a red-NIR phosphorescent rhenium octahedral cluster tetra-anion are associated electrostatically to generate a supramolecular ionic framework which crystallizes in the 1̄ centric space group. The emission properties of the hybrids are studied in the crystalline state and in solution revealing a resonant energy transfer and a high sensitivity toward oxygen.

Photoinduced electron transfer between a noble-metal-free [MoICl] cluster and polyoxometalates.

Evidence for photoinduced intermolecular electron transfer from the excited state of the [MoICl] electron-rich cluster to polyoxometalates (POMs) is reported. We demonstrate that the global charge density of POMs affects the efficiency of electron transfer. This work paves the way for the rational design of photocatalytic systems using cluster-based complexes as robust noble-metal-free photosensitizers.

From K[ReMoS(CN)] Solid Solution to Individual Cluster Complexes: Separation and Investigation of [ReMoS(CN)] and [ReMoS(CN)] Heterometallic Clusters.

A series of new cluster compounds with {ReMoS} and {ReMoS} cores has been obtained and investigated. The clusters with different Re/Mo ratios were isolated as individual compounds, which made it possible to study their spectroscopic and electrochemical properties. The geometry of the new clusters was studied using a combination of X-ray diffraction analysis, XAS and quantum chemical DFT calculations.

Game of Crowns: Na Is Coming! Red NIR-Emissive Hybrid Liquid Crystals Containing Discotic Crown Ethers and NaMoXCl (X = Cl or Br).

Molecular or supramolecular materials that can self-organize into columns such as discotic liquid crystals are of interest for several applications in the field of optoelectronics. We show in this work that red near-infrared (NIR)-emissive metal cluster compounds of general formula NaMoXCl (X = Cl or Br) can be readily complexed with discotic liquid crystals containing a crown ether. Three cavity sizes have been tested with crown ethers bearing 4, 5, or 6 oxygen atoms.

Electrophilic and nucleophilic gas phase reactivity of the Janus cluster-based anions [{MoCl}Cl□] (□ = lacuna).

The lacunary monocharged anion [{MoCli8}Cla5□] presents concomitantly a strongly electrophilic site and a nucleophilic one. This Janus character in terms of reactivity is confirmed by its gas phase reaction with [BrCsK] to form [{MoCli8}Cla5Br] and by its unusual self-reactivity leading to [{MoCli8}Cla6] dianions.

CsLnCuS (Ln = La-Nd, Sm-Tb): Synthesis, Crystal Structure, and Magnetic and Optical Properties.

This work reports the preparation of new quaternary sulfides CsLnCuS (Ln = La-Nd, Sm-Tb), their original crystal and electronic structures, and their magnetic properties. The sulfides were prepared using a reactive flux method from mixtures of LnS (EuS), CsS, CuS, and S. They crystallize in a new type of structure (2/ space group) and exhibit a layer-like crystal structure, which is a hybrid of those of the ACeCuS series (A = Cs, K) and that of KCeCuS.

Flexible and Transparent Luminescent Cellulose-Transition Metal Cluster Composites.

Red-NIR luminescent polymers are principally obtained from petroleum-based derivatives in which emitters, usually a critical raw material such as rare-earth or platinum group metal ions, are embedded. Considering the strong ecological impact of their synthesis and the major risk of fossil fuel energy shortage, there is an urgent need to find alternatives. We describe a luminescent nanocomposite based on red-NIR phosphorescent molybdenum nanoclusters, namely CsMoI(OCOCF), embedded in an eco-friendly cellulose biopolymer matrix that is obtained by a simple solvent casting technique.

From Solid-State Cluster Compounds to Functional PMMA-Based Composites with UV and NIR Blocking Properties, and Tuned Hues.

New nanocomposite materials with UV-NIR blocking properties and hues ranging from green to brown were prepared by integrating inorganic tantalum octahedral cluster building blocks prepared via solid-state chemistry in a PMMA matrix. After the synthesis by the solid-state chemical reaction of the K[{TaBr}Br] ternary halide, built-up from [{TaBr}Br] anionic building blocks, and potassium cations, the potassium cations were replaced by functional organic cations (Kat) bearing a methacrylate function. The resulting intermediate, (Kat)[{TaBr}Br], was then incorporated homogeneously by copolymerization with MMA into transparent PMMA matrices to form a brown transparent hybrid composite Ta@PMMA.

A review on functional nanoarchitectonics nanocomposites based on octahedral metal atom clusters (Nb, Mo, Ta, W, Re): inorganic 0D and 2D powders and films.

This review is dedicated to various functional nanoarchitectonic nanocomposites based on molecular octahedral metal atom clusters (Nb, Mo, Ta, W, Re). 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.

High performance {NbTaX}@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 K[{NbTaX }X ] 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.

Controlling the Deposition Process of Nanoarchitectonic Nanocomposites Based on {NbTaX} Octahedral Cluster-Based Building Blocks (X = 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.

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 [{NbCl}L] 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 Nb; L = HO and/or Cl). To do so, a combined experimental and theoretical investigation of edge-bridged [{NbCl}Cl(HO)] cluster unit series ( = 0, 4, 6; = 2, 3, 4; = 2, 3, 4) has been carried out. By using the K[{NbCl}Cl] starting solid-state precursor, we explored the behavior of the [{NbCl}Cl] 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 {NbCl}@PVP ( = 2 or 3).

Surface Plasmon Tunability of Core-Shell Au@Mo 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@Mo nanoparticles can be tuned from 2.

Evidence of the Ambipolar Behavior of Mo 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 Mo 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 Cs[{MoI}I] and those of thin films of the aqua-complex-based compound [{MoI}I(HO)]·HO were investigated through an in-depth photoelectrochemical study.

Joint Venture of Metal Cluster and Amphiphilic Cationic Minidendron Resulting in Near Infrared Emissive Lamellar Ionic Liquid Crystals.

Inorganic red-NIR emissive materials are particularly relevant in many fields like optoelectronic, bioimaging or solar cells. Benefiting from their emission in devices implies their integration in easy-to-handle materials like liquid crystals, whose long-range ordering and self-healing abilities could be exploited and influence emission. Herein, we present red-NIR emissive hybrid materials obtained with phosphorescent octahedral molybdenum cluster anions electrostatically associated with amphiphilic guanidinium minidendrons.

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.

Supramolecular Frameworks Based on Rhenium Clusters Using the Synthons Approach.

The reaction of the K[{ReS}(OH)]·8HO rhenium cluster salt with pyrazine (Pz) in aqueous solutions of alkaline or alkaline earth salts at 4 °C or at room temperature leads to apical ligand exchange and to the formation of five new compounds: [{ReS}(Pz)(OH)(HO)] (), [{ReS}(Pz)(OH)(HO)] (), (NO)[{ReS}(Pz)(OH)(HO)](Pz)·3HO (), [Mg(HO)][{ReS}(Pz)(OH)(HO)]·8.5HO (), and K[-{ReS}(Pz)(OH)(HO)]·8HO (). Their crystal structures are built up from - or -[{ReS}(Pz)(OH)(HO)] cluster units.

Synthesis, Structure, and Spectroscopic Study of Redox-Active Heterometallic Cluster-Based Complexes [ReMoSe(CN)].

The heterometallic cluster-based compound K[ReMoSe(CN)] was obtained by high-temperature reaction from a mixture of ReSe and MoSe in molten potassium cyanide. The redox behavior of the [ReMoSe(CN)] cluster anion was studied by cyclic voltammetry in aqueous and organic media showing two reversible one-electron-redox transitions with of -0.462 and 0.

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 {TaBr} 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 [{TaBr}L] cluster units (L = Br or HO, in solution and in the solid-state), redox states, and vibrational and absorption properties are still not well established. Using K[{TaBr}Br] as a starting precursor (i: inner and a: apical), we have investigated the behavior of the [{TaBr}Br] cluster unit in terms of oxidation properties and chemical modifications both in solution (water and organic solvent) and after recrystallization.

Evidencing ((-CH)N)[WI] red-NIR emission and singlet oxygen generation by two photon absorption.

We report the first proof of the ability of octahedral tungsten clusters to emit red-NIR light and to produce singlet oxygen upon two-photon absorption, in solution and in the solid-state. Such discoveries open new perspectives for tungsten cluster compounds in several fields like optoelectronics, photodynamic therapy, and bioimaging.

Expanding the Toolbox of Octahedral Molybdenum Clusters and Nanocomposites Made Thereof: Evidence of Two-Photon Absorption Induced NIR Emission and Singlet Oxygen Production.

Bright NIR phosphorescence from octahedral molybdenum clusters has been known since the 1980s. However, their behavior toward NIR excitation has never been investigated. Here we report their abilities to emit NIR light and produce singlet oxygen upon two-photon absorption.