Effect of the 1D/2D dimensionality in copper and silver thiolate coordination polymers on their photophysical properties.

A series of four new copper and silver-thiolate, [M(-SPhCOR)] (M = Cu, Ag and R = H, Me), coordination polymers is reported. The study shows that the hydrogen bonding between the carboxylic acids directs the formation of a 2D structure associated with poor photoemission, while the steric hindrance of the ester groups allows the assembly of a 1D network coupled with bright luminescence.

Gold(I)-Thiolate Coordination Polymers as Multifunctional Materials: The Case of Au(I)--Fluorothiophenolate.

Gold-sulfur interaction has vital importance in nanotechnologies and material chemistry to design functional nanoparticles, self-assembled monolayers, or molecular complexes. In this paper, a mixture of only two basic precursors, such as the chloroauric acid (HAu(III)Cl) and a thiol molecule (-fluorothiophenol (-HSPhF)), are used for the synthesis of gold(I)-thiolate coordination polymers. Under different conditions of synthesis and external stimuli, five different functional materials with different states of [Au(I)(-SPhF)] can be afforded.

Er doped nanoparticles as upconversion thermometer probes in confined fluids.

Non-contact temperature measurement at the nanoscale by photoluminescence using a nano-sensor in a confined fluid has been performed in the present work. Upconversion lanthanide-doped nanoparticles applied to ratiometric thermometry could be considered as a self-referenced nanosensor. Gadolinium orthovanadate (GdVO) nanoparticles doped with Yb and Er were synthesized and then dispersed in an ester-based fluid.

Tuning the 1D-2D dimensionality upon ligand exchange in silver thiolate coordination polymers with photoemission switching.

Silver nanoparticles are known and widely used for their antimicrobial activities. Nevertheless, once they are released into the natural or biological environments, they can become toxic with time, because of the dissolution of some Ag(I) ions that can then react with thiol-based molecules, such as glutathione and/or compete with copper proteins. These assumptions are based on the high affinity of the soft acid Ag(I) and the soft base thiolates and the exchange reactions that are involved in complex physiological media.

Luminescent and sustainable d coinage metal thiolate coordination polymers for high-temperature optical sensing.

The d coinage metal coordination polymers (CPs) are known to display photophysical properties which can be tuned depending on the functionality of the ligand. Three new CPs made of d coinage metals and methyl thiosalicylate, [M(-SPhCOMe)] (M = Cu, Ag, Au), are reported. They are all constructed from one-dimensional metal-sulfur networks, in which Cu and Ag are three-coordinated to sulfur atoms, whereas Au is only two-coordinated.

A chiral 3D silver(I)-benzenedithiolate coordination polymer exhibiting photoemission and non-linear optical response.

A new tridimensional metal-organic chalcogenolate, made of a 1,3-benzenedithiolate bridging ligand and Ag(I), [Ag(1,3-BDT)], is reported. This coordination polymer has good thermal stability in air and displays both photoluminescence properties and a second harmonic generation response.

Investigation of hydrodynamic cavitation induced reactive oxygen species production in microchannels via chemiluminescent luminol oxidation reactions.

Hydrodynamic cavitation was evaluated for its reactive oxygen species production in several convergent-divergent microchannel at the transition from micro to milli scale. Channel widths and heights were systematically varied to study the influence of geometrical parameters at the transitory scale. A photomultiplier tube was used for time-resolved photon detection and monitoring of the chemiluminescent luminol oxidation reactions, allowing for a contactless and in situ quantization of reactive oxygen species production in the channels.

Cyclic Solid-State Multiple Phase Changes with Tuned Photoemission in a Gold Thiolate Coordination Polymer.

The discovery of a universal memory that exhibits fast access speed, high-density storage, and non-volatility has fuelled research into phase-change materials over the past decades. In spite of the efficiency of the inorganic chalcogenides for phase-change random access memory (PCRAM), they still have some inherent drawbacks, such as high temperature required for phase change and difficulty to control the domain size of the phase change, because of their brittleness. Here we present a Au -thiolate coordination polymer which undergoes two successive phase changes on application of mild heating (<200 °C) from amorphous-to-crystalline1-to-crystalline2 phases.

Perspectives for CdSe/CdS spherical quantum wells as rapid-response nano-scintillators.

We explore the effect of the shell thickness on the time response of CdS/CdSe/CdS spherical quantum wells (SQWs) nanoscintillators under X-ray excitation. We first compare the spectral and timing properties under low and intense optical excitation, which allows us to identify the complex temporal and spectral response of the highly excited species. We find that a defect-induced delayed luminescence appears at large sizes.

Localization and quantification of radical production in cavitating flows with luminol chemiluminescent reactions.

Hydrodynamic cavitation experiments in microfluidic systems have been performed with an aqueous solution of luminol as the working fluid. In order to identify where and how much reactive radical species are formed by the violent bubble collapse, the resulting chemiluminescent oxidation reaction of luminol was scrutinized downstream of a constriction in the microchannel. An original method was developed in order to map the intensity of chemiluminescence emitted from the micro-flow, allowing us to localize the region where radicals are produced.

Transparent and luminescent glasses of gold thiolate coordination polymers.

Obtaining transparent glasses made of functional coordination polymers (CPs) represents a tremendous opportunity for optical applications. In this context, the first transparent and red-emissive glasses of gold thiolate CPs have been obtained by simply applying mechanical pressure to amorphous powders of CPs. The three gold-based CP glasses are composed of either thiophenolate [Au(SPh)] , phenylmethanethiolate [Au(SMePh)] or phenylethanethiolate [Au(SEtPh)] .

Molecules versus Nanoparticles: Identifying a Reactive Molecular Intermediate in the Synthesis of Ternary Coinage Metal Chalcogenides.

The identification of reactive intermediates during molecule-to-nanoparticle (NP) transformation has great significance in comprehending the mechanism of NP formation and, therefore, optimizing the synthetic conditions and properties of the formed products. We report here the room temperature (RT) synthesis of AgCuSe NPs from the reaction of di--butyl selenide with trifluoroacetates (TFA) of silver(I) and copper(II). The isolation and characterization of a molecular species during the course of this reaction, [AgCu(TFA)(BuSe)] (), which shows extraordinary reactivity and interesting thermochromic behavior (blue at 0 °C and green at RT), confirmed that ternary metal selenide NPs are formed via this intermediate species.

A New Lamellar Gold Thiolate Coordination Polymer, [Au(-SPhCOH)], for the Formation of Luminescent Polymer Composites.

The photoluminescence of gold thiolate clusters brings about many potential applications, but its origin is still elusive because of its complexity. A strategy in understanding the structure-properties relationship is to study closely related neutral gold thiolate coordination polymers (CPs). Here, a new CP is reported, [Au(-SPhCOH)].

Doping nanoparticles using pulsed laser ablation in a liquid containing the doping agent.

While doping of semiconductors or oxides is crucial for numerous technological applications, its control remains difficult especially when the material is reduced down to the nanometric scale. In this paper, we show that pulsed laser ablation of an undoped solid target in an aqueous solution containing activator ions offers a new way to synthesise doped-nanoparticles. The doping efficiency is evaluated for laser ablation of an undoped GdO target in aqueous solutions of EuCl with molar concentration from 10 mol L to 10 mol L.

New Lamellar Silver Thiolate Coordination Polymers with Tunable Photoluminescence Energies by Metal Substitution.

The structures of two lamellar silver thiolate coordination polymers [Ag( p-SPhCOH)] (1) and [Ag( p-SPhCOMe)] (2) are described for the first time. Their inorganic part is composed of distorted AgS honeycomb networks separated by noninterpenetrated thiolate ligands. The main difference between the two compounds arises from dimeric hydrogen bonds present for the carboxylic acids.

Structural Diversity of Coordination Polymers Based on a Heterotopic Ligand: Cu(II)-Carboxylate vs Cu(I)-Thiolate.

Two copper(II)-carboxylate disulfide coordination polymers [Cu((OCPhS))(HO)] (1, 2) and one copper(I)-thiolate coordination polymer [Cu( p-SPhCOH)] (3) have been synthesized using either the 4-mercaptobenzoic acid (HSPhCOH) or the 4,4'-dithiodibenzoic acid ((SPhCOH)) as ligand. These three compounds were characterized by X-ray diffraction, IR, and thermogravimetric analyses. Compounds 1 and 2 are polymorphs with the presence, for both, of dinuclear paddle-wheel copper(II)-carboxylates.

Intrinsic triple-emitting 2D copper thiolate coordination polymer as a ratiometric thermometer working over 400 K range.

A copper thiolate coordination polymer, [Cu(p-SPhCOMe)], is described and exhibits, under UV, luminescence thermochromism, associated to a unique well-separated triple emission. This compound is the most promising candidate as a ratiometric temperature sensor, working in a wide temperature range, from 100 to 500 K, with a great sensitivity.

Origin of the nano-carbon allotropes in pulsed laser ablation in liquids synthesis.

Carbon-based materials are of great technological and scientific interest in materials science. Pulsed laser ablation in liquids (PLAL) is extensively used as a method to produce nanoparticles including nanodiamond and related materials. In this feature article, we will review the use of PLAL to tackle the challenges of synthesizing carbon-based nanostructures.

Shedding light on an ultra-bright photoluminescent lamellar gold thiolate coordination polymer [Au(p-SPhCO2Me)]n.

The first structure elucidation of a lamellar gold thiolate coordination polymer is described. [Au(p-SPhCO2Me)]n is obtained from the simultaneous esterification of mercaptobenzoic acid and reduction of the Au(iii) precursor. Despite the presence of aurophilic interactions, the intense phosphorescence (QY ∼ 70%) originates from intra-ligand and metal-to-ligand transitions.

Atomistic Mechanisms for the Nucleation of Aluminum Oxide Nanoparticles.

A predictive model for nanoparticle nucleation has not yet been successfully achieved. Classical nucleation theory fails because the atomistic nature of the seed has to be considered. Indeed, geometrical structure as well as stoichiometry do not always match the bulk values.

Modelling energy deposition in nanoscintillators to predict the efficiency of the X-ray-induced photodynamic effect.

Scintillating nanoparticles (NPs) in combination with X-ray or γ-radiation have a great potential for deep-tissue cancer therapy because they can be used to locally activate photosensitizers and generate singlet oxygen in tumours by means of the photodynamic effect. To understand the complex spatial distribution of energy deposition in a macroscopic volume of water loaded with nanoscintillators, we have developed a GEANT4-based Monte Carlo program. We thus obtain estimates of the maximum expected efficiency of singlet oxygen production for various materials coupled to PS, X-ray energies, NP concentrations and NP sizes.

Autocorrelation analysis for the unbiased determination of power-law exponents in single-quantum-dot blinking.

We present an unbiased and robust analysis method for power-law blinking statistics in the photoluminescence of single nanoemitters, allowing us to extract both the bright- and dark-state power-law exponents from the emitters' intensity autocorrelation functions. As opposed to the widely used threshold method, our technique therefore does not require discriminating the emission levels of bright and dark states in the experimental intensity timetraces. We rely on the simultaneous recording of 450 emission timetraces of single CdSe/CdS core/shell quantum dots at a frame rate of 250 Hz with single photon sensitivity.

Novel barium-organic incorporated iodometalates: do they have template properties for constructing rare heterotrimetallic hybrids?

New barium-organic derivatives are introduced as countercations in the iodocuprates and -argentates to yield novel hybrids with unique structural motifs and bonding modes, many of them also showing vivid fluorescence on exposure to UV light. The tetrahedral MX4/trigonal-coplanar MX3 unit in these hybrids [Ba2(DMSO)12Cu8I12] (1) and [Ba(tetraglyme)2]2[Ag8I12]·EtOH (7) can be replaced by the M'I4/M'I3 unit without compromising their basic structural motifs, thus leading to the formation of the rare mixed Cu-Ag iodometalates [Ba2(DMSO)12Cu4Ag4I12] (9) and [Ba(tetraglyme)2]2[CuAg7I12]·EtOH (10), respectively. In contrast, a breakdown in the structure-directing properties of these iodometalates was observed in the mixed Ag-Pb iodometalate [Ba(tetraglyme)2]2[Pb2Ag2I10]·2Me2CO (11), where the basic structure of the synthon [Ba(tetraglyme)2]2[Ag4I8] (8) was not retained due to the compulsory molecular rearrangement required as a result of replacing AgI4/AgI3 units with octahedral PbI6 units.

Direct synthesis of hexagonal NaGdF₄ nanocrystals from a single-source precursor: upconverting NaGdF₄ :Yb³⁺ ,Tm³⁺ and its composites with TiO₂ for near-IR-driven photocatalysis.

A novel single-source precursor NaGd(TFA)4 (diglyme) (TFA=trifluoroacetate) was synthesized, characterized thoroughly, and used to obtain the hexagonal phase of NaGdF4 nanoparticles as an efficient matrix for lanthanide-doped upconverting nanocrystals (NCs) that convert near-infrared radiation into shorter-wavelength UV/visible light. These NCs were then used to prepare well-characterized TiO2@NaGdF4:Yb(3+),Tm(3+) nanocomposites to extend the absorption range of the TiO2 photocatalyst from the UV to the IR region. While the visible/near IR part of the photoluminescent spectra remains almost unaffected by the presence of TiO2, the UV part is strongly quenched due to the absorption of TiO2 above its gap at approximately 380 nm by energy transfer or FRET.

γ-Al2O3 nanoparticles synthesised by pulsed laser ablation in liquids: a plasma analysis.

Pulsed laser ablation has proved its reliability for the synthesis of nano-particles and nano-structured materials, including metastable phases and complex stoichiometries. The possible nucleation of the nanoparticles in the gas phase and their growth has been little investigated, due to the difficulty of following the gas composition as well as the thermodynamic parameters. We show that such information can be obtained from the optically active plasma during its short lifetime, only a few microseconds for each laser pulse, as a result of a quick quenching due to the liquid environment.