Mechanoresponsive luminescence triggered by phase transition of a supercooled copper(I) complex.

Under mechanical stimulation, a copper(I) complex in its supercooled liquid state transforms into a crystalline phase, showing a dramatic emission color change from red to green that is accompanied by a 20-fold increase in the photoluminescence quantum yield up to 87%. This reversible phase transition relies on the intriguing ability of this copper complex to form a supercooled metastable state.

Cubane Dimerization: Cu4 vs Cu8 Copper Iodide Clusters.

Copper(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 [Cu4I4] cubane geometry is reported. Among them, [Cu8I8] octanuclear clusters of rare geometry resulting from dimerization of the tetranuclear counterparts were also synthesized. Two different phosphine ligands were studied, bearing either a styrene or an ethyl group. Therefore, the effect of the dimerization and of the ligand nature on the photophysical properties of the resulting clusters is investigated. The structural differences were analyzed by single-crystal X-ray diffraction (SCXRD), solid-state nuclear magnetic resonance (NMR), infrared, and Raman analyses. Compared to the ethyl group, the styrene function appears to greatly impact the photophysical properties of the clusters. The luminescence thermochromic properties of the ethyl derivatives and the intriguing photophysical properties of the clusters with styrene function were rationalized by density functional theory (DFT) calculations. Thus, the styrene group significantly lowers in energy the vacant orbitals and consequently affects the global energetic layout of the clusters. From this study, it was found that the nuclearity of copper iodide clusters eventually has less influence on the photophysical properties than the nature of the ligand. The design of proper ligands should therefore be considered when developing materials for specific lighting applications.

Photoactive CuI-Cross-Linked Polyurethane Materials.

Using 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. The luminescence thermochromism is characterized by a change in the wavelength and intensity of the emission with temperature, and the vapochromic effect presents a contrasted response of extinction or exaltation according to the nature of the solvent of exposure. By combining the luminescence characteristics of photoactive copper iodide complexes with the ease of polymer processing, the application of these luminescent materials as phosphors in LED (light-emitting diode) devices was also demonstrated. The present study shows that the use of copper iodide complexes as cross-linkers in polymeric materials is a relevant strategy to design materials with enhanced functionalities in addition to their low cost and sustainable characteristics.

Copper Iodide Clusters Coordinated by Emissive Cyanobiphenyl-Based Ligands.

Copper(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 [Cu4I4L4] (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. The emissive properties of the ligands have a great impact onto the photophysical properties of the cluster. Compared with classical [Cu4I4L4] copper iodide clusters, the origin of the emission bands is largely modified. The CBP moiety of electron acceptor character significantly lowers in energy the vacant orbitals and consequently affects the global energetic layout. These clusters present dual emission based on two different emissive centers which interplay through energy transfer. This study demonstrates that the design of original ligands is an effective approach to enrich the photophysical properties of the appealing family of copper halide complexes.

Molecular copper iodide clusters: a distinguishing family of mechanochromic luminescent compounds.

Mechanochromic 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 [Cu4I4L4] (L = organic ligand) stand out. Indeed, they can exhibit multiple luminescent stimuli-responsive properties, being particularly suitable for the development of multifunctional photoactive systems. This perspective describes the survey of these mechanochromic luminescent cubane copper iodide clusters. Based on our investigations, their mechanochromic luminescence properties are presented along with the study of the underlying mechanism. Establishment of structure-property relationships supported by various characterization techniques and associated with theoretical investigations permits gaining insights into the mechanism at play. Studies of other researcher groups are also described and illustrate the interest shown by these mechanochromic compounds. Mechanically responsive films are reported, demonstrating their potential use in a range of applications of such copper-based stimuli-responsive materials. Current challenges faced by the development of technological applications are finally outlined.

Combining Theory and Experiment to Get Insight into the Amorphous Phase of Luminescent Mechanochromic Copper Iodide Clusters.

In 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 [Cu4I4[PPh2(C6H4-CH2OH)]4] (1) are reported in this study. This compound can form upon melting an amorphous phase, giving an unprecedented opportunity to investigate the mechanochromism phenomenon. Because the mechanically induced crystalline-to-amorphous transition is only partial, the completely amorphous phase represents the ultimate state of the mechanically altered phase. Furthermore, the studied compound could form two different crystalline polymorphs, namely, [Cu4I4[PPh2(C6H4-CH2OH)]4]·C2H3N (1·CH3CN) and [Cu4I4[PPh2(C6H4-CH2OH)]4]·3C4H8O (1·THF), allowing the establishment of straightforward structure-property relationships. Photophysical and structural characterizations of 1 in different states were performed, and the experimental data were supported by theoretical investigations. Solid-state NMR analysis permitted quantification of the amorphous part in the mechanically altered phase. IR and Raman analysis enabled identification of the spectroscopic signatures of each state. Density functional theory calculations led to assignment of both the NMR characteristics and the vibrational bands. Rationalization of the photoluminescence properties was also conducted, with simulation of the phosphorescence spectra allowing an accurate interpretation of the thermochromic luminescence properties of this family of compounds. The combined study of crystalline polymorphism and the amorphous state allowed us to get deeper into the mechanochromism mechanism that implies changes of the [Cu4I4] cluster core geometry. Through the combination of multistimuli-responsive properties, copper iodide clusters constitute an appealing class of compounds toward original functional materials.

Polymorphic Copper Iodide Anions: Luminescence Thermochromism and Mechanochromism of (PPh4)2[Cu2I4].

The photoluminescent stimuli-responsive properties of two crystalline polymorphs with the formula (PPh4)2[Cu2I4] 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. The establishment of structure-properties relationships, supported by a theoretical approach, permits us to get insights into the origin of the photoluminescence properties and the mechanisms at play. According to DFT calculations, the different emission bands originate either from the (PPh4)+ organic cation or from the [Cu2I4]2- anion. Activation of these two emissive centers appears to be dependent on the crystalline packing of the polymorph. The thermochromism displayed by one polymorph can be attributed to a variation in temperature of the relative intensities of two emission bands of two different excited states. The origin is different for the other polymorph, with emission bands coming from two independent emissive centers: namely, (PPh4)+ and [Cu2I4]2-. The luminescence mechanochromism is attributed to a polymorphic transition. The mechanical solicitation induces a partial transformation of one polymorph into the other within a disordered phase. The mechanochromic mechanism can be related to mechanical modifications of intermolecular interactions between the (PPh4)+ cations. By displaying luminescence properties that depend on crystalline structure, excitation wavelength, temperature, and mechanical solicitation, the studied copper iodides offer a great possibility of emissive color control and switching, a clear demonstration of the great potentialities of this family of compounds for the development of photoactive materials.

Aggregation-Induced Emission Properties of Copper Iodide Clusters.

The aggregation-induced emission (AIE) properties of two different copper iodide clusters have been studied. These two [Cu4 I4 L4 ] 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. The formed particles present luminescent thermochromism comparable to that of the bulk compounds. The observed AIE properties can be attributed to suppression of nonradiative relaxation of the excited states in a more rigid state, in relation to the large structural relaxation of the excited triplet state. The differences observed in the AIE properties of the two clusters can be related to the different ligands. A correlation between the luminescence mechanochromic properties and the AIE effect is not straightforward, but the formation of "soft" molecular solids is a common characteristic that can explain the photoactive properties of these compounds.

Luminescence mechanochromism of copper iodide clusters: a rational investigation.

The 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 [Cu4I4L4] (L = organic ligand) clusters have been attributed to modifications of cuprophilic interactions induced by mechanical solicitation. In this study, we ascertain our hypothesis by choosing to study the luminescence mechanochromism of a [Cu4I4(PPh3)4] cluster which presents two crystalline polymorphs exhibiting strikingly different Cu-Cu bond lengths. As forecasted, only one of these two polymorphs exhibits mechanochromic properties. Structural and optical characterization methods are reported along with structural characterization under controlled pressure allowing a precise analysis of the structural changes occurring under mechanical stress. In addition to confirming our mechanism based on enhancement of cuprophilic interactions under pressure, this study demonstrates the possibility of prediction of mechanochromic properties in the family of copper iodide compounds that constitutes a step further toward the rational design of stimuli-responsive materials.

A Heptanuclear Copper Iodide Nanocluster.

Nanoscale 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. This nanometer-size cluster is formulated as [Cu7I7(P(C6H4CF3)3)6(CH3CN)] and its novel structure has been characterized by X-ray diffraction and multinuclear solid-state 63Cu, 31P, 13C, 19F, and 1H NMR spectroscopy. The photoluminescence properties of this cluster have been studied at variable temperature. Density functional theory calculations have been performed on this large molecular structure and allow one to rationalize the observed luminescence properties. This study highlights the crucial role of cuprophilic interactions in molecular copper iodide clusters for exhibiting photoactive properties.

Luminescence Vapochromism of a Dynamic Copper Iodide Mesocate.

A copper iodide complex coordinated by three phosphine ligands with the formula [Cu2 I2 (Ph2 PC2 (C6 H4 )C2 PPh2 )3 ] 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.

Evaluation of Ligands Effect on the Photophysical Properties of Copper Iodide Clusters.

Luminescent 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 [Cu4I4L4] (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. We thus report here, the comparative study of a series of cubane copper iodide clusters coordinated by different phosphine ligands, with the goal of analyzing the effect of the ligands nature on the photoluminescence properties. The synthesis, structural, and photophysical characterizations along with theoretical investigations of copper iodide clusters with ligands presenting different electronic properties, are described. A method to simplify the analysis of the 31P solid-state NMR spectra is also reported. While clusters with electron-donating groups present classical luminescence properties, the cluster bearing strong electron-withdrawing substituents exhibits original behavior demonstrating a clear influence of the ligands properties. In particular, the electron-withdrawing character induces a decrease in energy of the unoccupied molecular orbitals, that consequently impacts the emission properties. The modification of the luminescence thermochromic properties of the clusters are supported by density functional theory (DFT) calculations. This study demonstrates that the control of the luminescence properties of these compounds can be achieved through modification of the coordinated ligands, nevertheless the role of the crystal packing should not be underestimated.

Luminescence Mechanochromism Induced by Cluster Isomerization.

Luminescent 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 [Cu4I4(PPh3)4] copper iodide cluster presenting a chair geometry, being an isomer of the most common cubane form. This molecular cluster formulated [Cu4I4(PPh3)4]·2CHCl3 (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. In order to understand the underlying mechanism, a comparison with two related compounds has been conducted. The first one is a pseudopolymorph of 1 formulated as [Cu4I4(PPh3)4]·CH2Cl2 (2), which exhibits luminescent mechanochromic properties as well. The other one is also a chair compound but with a slightly different phosphine ligand, namely, [Cu4I4(PPh2C6H4CO2H)4] (3), lacking mechanochromic properties. Structural and optical characterizations of the clusters have been analyzed in light of previous electronic structure calculations. The results suggest an unpreceded mechanochromism phenomenon based on a solid-state chair → cubane isomer conversion. This study shows that polynuclear copper iodide compounds are particularly relevant for the development of luminescent mechanochromic materials.

Ion-shaping of embedded gold hollow nanoshells into vertically aligned prolate morphologies.

Ion 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. Samples have been irradiated with 74 MeV Kr ions at room temperature and for increasing fluences up to 3.8 × 10(14) cm(-2). In parallel, the experimental results have been theoretically simulated by using a three-dimensional code based on the thermal-spike model. These calculations show that the particles undergo a partial melting during the ion impact, and that the amount of molten phase is maximal when the impact is off-center, hitting only one hemisphere of the hollow nano-particle. We suggest a deformation scenario which differs from the one that is generally proposed for solid nano-particles. Finally, these functional materials can be seen as building blocks for the fabrication of nanodevices with really three-dimensional architecture.

Pressure Control of Cuprophilic Interactions in a Luminescent Mechanochromic Copper Cluster.

For 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.

Geometry flexibility of copper iodide clusters: variability in luminescence thermochromism.

An 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. A new polymorph of the cubane [Cu4I4(PPh3)4] cluster is indeed presented (3). The structural differences of the clusters were analyzed by solid-state nuclear magnetic resonance spectroscopy. Luminescence properties of the three clusters were studied in detail as a function of the temperature showing reversible luminescence thermochromism for 1 with an intense orange emission at room temperature. This behavior presents different feature compared to the cubane cluster and completely contrasts with the open isomer, which is almost nonemissive at room temperature. Indeed, the thermochromism of 1 differs by a concomitant increase of the two emission bands by lowering the temperature, in contrast to an equilibrium phenomenon for 3. The luminescence properties of 2 are very different by exhibiting only one single band when cooled. To rationalize the different optical properties observed, density functional theory calculations were performed for the three clusters giving straightforward explanation for the different luminescence thermochromism observed, which is attributed to different contributions of the ligands to the molecular orbitals. Comparison of 3 with its [Cu4I4(PPh3)4] cubane polymorphs highlights the sensibility of the emission properties to the cuprophilic interactions.

Mechanochromic luminescence of copper iodide clusters.

Luminescent 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. The local disruption of the crystal packing induces changes in the cluster geometry and in particular the modification of the cuprophilic interactions, which consequently modify the emissive states. This study constitutes a step further toward the understanding of the mechanism involved in the mechanochromic luminescent properties of multimetallic coordination complexes.

Polymorphic copper iodide clusters: insights into the mechanochromic luminescence properties.

An 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. Interestingly, the photophysical properties of the resulting partially amorphous crushed compound are closed to those of the other yellow polymorph. Comparative structural and optical analyses of the different phases including a solution of clusters permit us to establish a correlation between the Cu-Cu bond distances and the luminescence properties. In addition, the local structure of the [Cu4I4P4] cluster cores has been probed by (31)P and (65)Cu solid-state NMR analysis, which readily indicates that the grinding process modifies the phosphorus and copper atoms environments. The mechanochromic phenomenon is thus explained by the disruption of the crystal packing within intermolecular interactions inducing shortening of the Cu-Cu bond distances in the [Cu4I4] cluster core and eventually modification of the emissive state. These results definitely establish the role of cuprophilic interactions in the mechanochromism of copper iodide clusters. More generally, this study constitutes a step further into the understanding of the mechanism involved in the mechanochromic luminescent properties of metal-based compounds.

Single KTP nanocrystals as second-harmonic generation biolabels in cortical neurons.

We 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.