Hybrid copper(I) halide materials are currently attracting significant attention due to their exceptional luminescence properties, offering great potential for the development of multifunctional emissive materials with, in addition, eco-friendly features. A binuclear copper iodide complex, based on the [CuIL] motif with phosphite derivatives as ligands, has been synthesized and structurally characterized. Photophysical investigations indicate that this complex displays luminescence thermochromic properties, which are characterized by a temperature-dependent change in the relative intensity of two emission bands.
View Article and Find Full Text PDFCopper(I) halides are well-known for their structural diversity and rich photoluminescence properties, showing great potential for the development of solid-state lighting technology. A series of four molecular copper iodide clusters based on the [CuI] cubane geometry is reported. Among them, [CuI] octanuclear clusters of rare geometry resulting from dimerization of the tetranuclear counterparts were also synthesized.
View Article and Find Full Text PDFUsing multinuclear copper iodide complexes as cross-linking agents in a polyurethane matrix, original photoluminescent stimuli-responsive materials were synthesized. The intrinsic photoluminescence properties of the covalently incorporated copper iodide complexes are thus transferred to the materials while retaining the beneficial characteristics of the polymer host. The transparent materials exhibit room-temperature phosphorescence with emission switching properties by displaying luminescence thermochromism and solvatochromism.
View Article and Find Full Text PDFCopper(I) halides are currently the subject of intensive research because of their rich photophysical properties combined with economic and eco-friendly advantages for practical applications. The molecular copper iodide cluster of the general formula [CuIL] (L = ligand) is a well-known photoluminescent compound, and the possibility to enlarge the panel of its photophysical properties is studied here, by exploring ligands bearing a distinct emitter. The comparative study of five copper iodide clusters coordinated by different phosphine ligands functionalized by the emissive cyanobiphenyl (CBP) group is thus described in this work.
View Article and Find Full Text PDFMechanochromic luminescent materials displaying switchable luminescence properties in response to external mechanical force are currently attracting wide interest because of their multiple potential applications. In the growing number of mechanochromic luminescent compounds, mechanochromic complexes based on copper present appealing features with a large variety of mechanochromic properties and economical advantages over other metals. Among Cu-based compounds, molecular copper iodide clusters of cubane geometry with formula [CuIL] (L = organic ligand) stand out.
View Article and Find Full Text PDFIn the field of stimuli-responsive luminescent materials, mechanochromic compounds exhibiting reversible emission color changes activated by mechanical stimulation present appealing perspectives in sensor applications. The mechanochromic luminescence properties of the molecular cubane copper iodide cluster [CuI[PPh(CH-CHOH)]] () are reported in this study. This compound can form upon melting an amorphous phase, giving an unprecedented opportunity to investigate the mechanochromism phenomenon.
View Article and Find Full Text PDFThe photoluminescent stimuli-responsive properties of two crystalline polymorphs with the formula (PPh)[CuI] are reported. Distinct luminescence properties are exhibited by these ionic copper iodide compounds with blue or yellow emission, and original luminescence thermochromism and mechanochromism are demonstrated. While one polymorph displays contrasted temperature-dependent emission properties, the other shows great modification of its emission upon mechanical solicitation.
View Article and Find Full Text PDFThe aggregation-induced emission (AIE) properties of two different copper iodide clusters have been studied. These two [Cu I L ] clusters differ by their coordinated phosphine ligand and the luminescent mechanochromic properties are only displayed by one of them. The two clusters are AIE-active luminophors that exhibit an intense emission in the visible region upon aggregation.
View Article and Find Full Text PDFThe development of luminescent mechanochromic materials depends mainly on the possibility to rationally design them with the desired properties. Molecular copper iodide clusters constitute an unprecedented family of compounds exhibiting great changes of their luminescence properties upon mechanical stress. From previous studies, the mechanochromic properties of cubane [CuIL] (L = organic ligand) clusters have been attributed to modifications of cuprophilic interactions induced by mechanical solicitation.
View Article and Find Full Text PDFA copper iodide complex coordinated by three phosphine ligands with the formula [Cu I (Ph PC (C H )C PPh ) ] exhibits solvatochromic and vapochromic luminescence properties. A mechanism based on solvent-dependent molecular motion appears to occur. The highly contrasted response observed upon THF solvent exposure makes this complex an appealing candidate for chemical sensor applications.
View Article and Find Full Text PDFNanoscale molecular clusters are attractive for the design of materials exhibiting original functions and properties. In particular, copper iodide clusters of high nuclearity are well-known for their stimuli-responsive luminescence properties. The synthesis and characterization of an unprecedented copper(I) iodide molecular cluster based on an original heptanuclear inorganic core are reported.
View Article and Find Full Text PDFLuminescent materials based on copper complexes are currently receiving increasing attention because of their rich photophysical properties, opening a wide field of applications. The copper iodide clusters formulated [CuIL] (L = ligand), are particularly relevant for the development of multifunctional materials based on their luminescence stimuli-responsive properties. In this context, controlling and modulating their photophysical properties is crucial and this can only be achieved by thorough understanding of the origin of the optical properties.
View Article and Find Full Text PDFLuminescent mechanochromic materials exhibiting reversible changes of their emissive properties in response to external mechanical forces are currently emerging as an important class of stimuli-responsive materials because of promising technological applications. Here, we report on the luminescence mechanochromic properties of a [CuI(PPh)] copper iodide cluster presenting a chair geometry, being an isomer of the most common cubane form. This molecular cluster formulated [CuI(PPh)]·2CHCl (1) exhibits a highly contrasted emission response to manual grinding, and, interestingly, the optical properties of the ground phase present striking similarities with those of the cubane isomer.
View Article and Find Full Text PDFIon beam shaping is a novel technique with which one can shape nano-structures that are embedded in a matrix, while simultaneously imposing their orientation in space. In this work, we demonstrate that the ion-shaping technique can be implemented successfully to engineer the morphology of hollow metallic spherical particles embedded within a silica matrix. The outer diameter of these particles ranges between 20 and 60 nm and their shell thickness between 3 and 14 nm.
View Article and Find Full Text PDFFor the development of applications based on mechanochromic luminescent materials, a comprehensive study of the mechanism responsible for the emission changes is required. We report the study of a mechanochromic copper iodide cluster under hydrostatic pressure, which allows control of crystal packing via modification of the intermolecular interactions. In situ single-crystal powder X-ray diffraction analysis and emission measurements under pressure permit one to establish a direct correlation between the molecular structure and luminescence properties and, in particular, to demonstrate that cuprophilic interactions are responsible for the stimuli-responsive luminescence properties of such multinuclear coordination compounds.
View Article and Find Full Text PDFAn original copper(I) iodide cluster of novel geometry obtained by using a diphosphine ligand is reported and is formulated [Cu6I6(PPh2(CH2)3PPh2)3] (1). Interestingly, this sort of "eared cubane" cluster based on the [Cu6I6] inorganic core can be viewed as a combination of the two known [Cu4I4] units, namely, the cubane and the open-chair isomeric geometries. The synthesis, structural and photophysical characterisations, as well as theoretical study of this copper iodide along with the derived cubane (3) and open-chair (2) [Cu4I4(PPh3)4] forms, were investigated.
View Article and Find Full Text PDFLuminescent mechanochromic materials are particularly appealing for the development of stimuli-responsive materials. Establishing the mechanism responsible for the mechanochromism is always an issue owing to the difficulty in characterizing the ground phase. Herein, the study of real crystalline polymorphs of a mechanochromic and thermochromic luminescent copper iodide cluster permits us to clearly establish the mechanism involved.
View Article and Find Full Text PDFAn in-depth study of mechanochromic and thermochromic luminescent copper iodide clusters exhibiting structural polymorphism is reported and gives new insights into the origin of the mechanochromic luminescence properties. The two different crystalline polymorphs exhibit distinct luminescence properties with one being green emissive and the other one being yellow emissive. Upon mechanical grinding, only one of the polymorphs exhibits great modification of its emission from green to yellow.
View Article and Find Full Text PDFWe report an efficient colloidal synthesis of KTiOPO4 (KTP) nanocrystals with excellent crystallinity and the direct observation of optical second-harmonic generation (SHG) from discrete KTP nanocrystals in neurons cultured from mammalian brain cortex. Direct internalization and monitoring of these nanoparticles was successfully achieved without limitations from cytotoxicity, bleaching and blinking emission.
View Article and Find Full Text PDFTitanium dioxide is a well known photocatalyst for reactions involving surface trapped photogenerated carriers. Noble metal photo-reduction may be used for the processing of silver/TiO(2) nanocomposite coatings that may exhibit interesting optical and electrical properties. We present here results of our investigations performed on an original system consisting of preformed colloidal TiO(2) nanoparticles homogeneously dispersed within a mesoporous silica host matrix.
View Article and Find Full Text PDFA copper iodide cluster bearing reactive silanol groups exhibits thermochromic luminescence properties sensitive to its chemical environment and is thus a suitable building block for the synthesis of optically active materials.
View Article and Find Full Text PDFWe investigate the role of capillarity stresses on the ion-hammering phenomenon when sub-micrometer colloidal particles are considered. To this end, nearly monodisperse, chemically synthesized silica (SiO₂) colloids (100, 300 and 600 nm) were irradiated at room temperature (300 K) with 4 MeV Au ions for fluences up to Φ = 1.8 × 10¹⁶ cm⁻².
View Article and Find Full Text PDFThree copper(I) iodide clusters coordinated by different phosphine ligands formulated [Cu(4)I(4)(PPh(3))(4)] (1), [Cu(4)I(4)(Pcpent(3))(4)] (2), and [Cu(4)I(4)(PPh(2)Pr)(4)] (3) (PPh(3) = triphenylphosphine, Pcpent(3) = tricyclopentylphosphine, and PPh(2)Pr = diphenylpropylphosphine) have been synthesized and characterized by (1)H and (31)P NMR, elemental analysis and single crystal X-ray diffraction analysis. They crystallize in different space groups, namely, monoclinic P21/c, cubic Pa ̅3, and tetragonal I ̅42m for 1, 2, and 3, respectively. The photoluminescence properties of clusters 1 and 3 show reversible luminescence thermochromism with two highly intense emission bands whose intensities are temperature dependent.
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