Experimental measurement of local high temperature at the surface of gold nanorods using doped ZnGa2O4 as a nanothermometer.

Heat measurement induced by photoexcitation of a plasmonic metal nanoparticle assembly under environmental conditions is of primary importance for the further development of applications in the fields of (photo)catalysis, nanoelectronics and nanomedicine. Nevertheless, the fine control of the rise in temperature remains difficult and limits the use of this technology due to the lack of local temperature measurement tools working under environmental conditions. Luminescence nanothermometers are an alternative solution to the limitations of conventional contact thermometers since they are able to give an absolute temperature value with high spatial resolution using common optical equipment. As a proof of concept of this nanothermometry approach, a high local temperature exceeding one hundred degrees is measured on the thermalized photoexcited aggregate of gold nanorods using ZnGa2O4:Cr3+,Bi3+ nanothermometers that have a strong temperature dependence on the luminescence lifetime of chromium(iii) and high sensitivity over an extensive range of temperatures. A study on the influence of the average distance between nanosensors and nanoheaters on the measured temperature is carried out by coating the nanosensors with a silica layer of tunable thickness, highlighting the temperature gradient at the vicinity of the nanoheater as the theory predicts. The variation of the optical nanosensor response is relevant and promising, and it could be further envisioned as a potential candidate for local temperature measurement at the nanoscale since no plasmonic effect on Cr3+ lifetime is observed. The results reported here open up an even wider field of application for high temperature nanothermometry on real samples such as aggregate particles for many applications including catalysis and nanoelectronics. Thermometry using luminescent nanoprobes, which is complementary to thermal microscopy techniques, will allow in situ and in operando temperature monitoring at very small scales.

Tuning the Oxidation States of Dopants: A Strategy for the Modulation of Material Photoluminescence Properties.

Doped single-phase materials have been widely investigated owing to their easy to implement synthesis and the variety of their properties. This Minireview covers strategies for the co-stabilization and the ratio control of several oxidation states of dopants inserted in the same host. The tuning of the oxidation states of dopants opens up many possibilities for the optimization of specific properties and can be envisioned for various applications such as telecommunication, medicine, displays, lasers or lighting. Technics used for the quantification of each valence state of dopant are also emphasized, and the importance of high throughput methods for the discovery of efficient materials with dopants in multiple valence states is discussed.

A coordinatively unsaturated iridium complex with an unsymmetrical redox-active ligand: (spectro)electrochemical and reactivity studies.

Redox-active ligands, owing to their electron reservoir capability, are well suited for the generation of coordinatively unsaturated metal complexes. We present here iridium complexes with an unsymmetrically substituted o-phenylenediamine ligand. A coordinatively unsaturated, formally iridium(iii) complex with the fully reduced o-phenylenediamide (or o-diamidobenzene) ligand was isolated and structurally characterized. This coordinatively unsaturated metal complex undergoes methylation reactions with a CH3+ source to form a new species with an Ir-CH3 bond. The redox-active Ir-CH3 complex performs the activation of CDCl3. The same activation reaction was also tested for other haloforms. In all types of reactions, the masked coordination site at the metal center and the electron reservoir behavior of the redox-active ligand are used for reactivity. Furthermore, we show that the aforementioned iridium(iii) complex performs redox-induced dihydrogen activation. This activation process was used to catalytically transfer the electrons and protons of dihydrogen to a substrate molecule. Crystallographic, spectroscopic, electrochemical, spectroelectrochemical and DFT methods were used to elucidate the geometric and the electronic structures of the metal complex in the various redox forms and to probe the mechanism of the investigated reactions. We demonstrate here how the cooperative behavior between a catalytically active metal center and a redox non-innocent ligand can be utilized to perform substrate bond activation and transformation.

MgTiO3:Mn4+ a multi-reading temperature nanoprobe.

MgTiO3 nanoparticles doped with Mn4+, with homogeneous size ranging about 63.1 ± 9.8 nm, were synthesized by a molten salt assisted sol gel method. These nanoparticles have been investigated as optical thermal sensors. The luminescence of tetravalent manganese ion in octahedral environment within the perovskite host presents drastic variations with temperature. Three different thermometry approaches have been proposed and characterized. Two luminescence intensity ratios are studied. Firstly between the two R-lines of Mn4+ emission at low temperature (-250 °C and -90 °C) with a maximal sensitivity of 0.9% °C-1, but also secondly between 2E → 4A2 (R-line) and the 4T2 → 4A2 transitions. This allows studying the temperature variation within a larger temperature range (-200 °C to 50 °C) with a sensitivity between 0.6% °C-1 and 1.2% °C-1 over this range. The last proposed method is the study of the lifetime variation versus temperature. The effective lifetime value corresponds to a combination of transitions from two excited energy levels of the tetravalent manganese (2E and 4T2) in thermal equilibrium toward the fundamental 4A2 state. Since the more energetic transition (4T2 → 4A2) is spin-allowed, contrary to the 2E → 4A2 one, the lifetime drastically decreases with the increase in temperature leading to an impressive high sensitivity value of 4.1% °C-1 at 4 °C and an exceptional temperature resolution of 0.025 °C. According to their optical features, MgTiO3:Mn4+ nanoparticles are indeed suitable candidates for the luminescence temperature probes at the nanoscale over several temperature ranges.

Electrocatalytic Dihydrogen Production with a Robust Mesoionic Pyridylcarbene Cobalt Catalyst.

A Co(III) complex with a mesoionic pyridylcarbene ligand is presented. This complex is an efficient electrocatalyst for H2 production at very low overpotential and high turnovers when using a (glassy carbon) GC electrode. The corresponding triazole complexes display no catalytic activity whatsoever under identical conditions. The remarkable robustness of the Co-C(carbene) bond towards acids is likely responsible for the high efficiency of this catalyst. The present results thus open new avenues for carbene-based ligands for generating functional models for hydrogenases.