Colorimetric Monitoring of a Chemical Reaction Using Cesium Lead Halide Assays

Cesium lead halide (CsPbX3, X = F, Cl, Br, I ) nanomaterials have a number of novel optoelectronic and physical properties, both of which are tailorable based on halide type and concentration, such as halide composition-dependent photoluminescence and rapid halide exchange while maintaining crystal structure. In this work we take advantage of these properties and use colloidal CsPbI3 nanoparticles as a proxy and colorimetric sensor of a chemical reaction in real-time. A solvolysis reaction between 2-bromo-2-methylbutane and butanol was used as a model system. A product of reaction, a bromide ion, could be detected via halide exchange with CsPbI3, by way of a quantitative blue shift (Δλ) in photoluminescence. The kinetics of this shift was calibrated against a known Br - source, which allowed for conversion to apparent values solvation kinetics. The observed rate constants (k) and corresponding activation energies (Ea) measured via the CsPbI3 probe were consistent with literature values for the reaction, confirming the validity of the approach.

Effect of PbSO4-Oleate Coverage on Cesium Lead Halide Perovskite Quantum Dots to Control Halide Exchange Kinetics

The selective control of halide ion exchange in metal halide perovskite quantum dots (PQDs) plays an important role in determining their band gap and composition. In this study, CsPbX3 (X = Cl−, Br−, and I−) PQDs were self-assembled with PbSO4-oleate to form a peapod-like morphology to selectively control halide ion exchange. Considering the distinct absorption and bright luminescence characteristics of these PQDs, in situ UV-Vis. absorption and fluorescence spectroscopies were employed to monitor the time-dependent band gap and compositional changes of the PQDs. We determined that the halide exchange in the capped PQDs is hindered—unlike the rapid anion exchange in noncapped PQDs—by a reduction in the halide exchange kinetic rate depending on the extent of coverage of the PQDs. Thus, we tracked the halide ion exchange kinetics between CsPbBr3 and CsPbI3 PQDs, depending on the coverage, using in situ UV-Vis. absorption/photoluminescence spectroscopy. We regulated the halide exchange reaction rate by varying the capping reaction temperature of the PQDs. The capping hindered the halide exchange kinetics and increased the activation energy. These results will enable the development of white LEDs, photovoltaic cells, and photocatalysts with alternative structural designs based on the divalent composition of CsPbX3 PQDs.

Synthesis and coordination chemistry of silver(I), gold(I) and gold(III) complexes with picoline-functionalized benzimidazolin-2-ylidene ligands

The reactions of N-alkyl-N′-picolyl-benzimidazolium bromides or N,N′-dipicolyl-benzimidazolium bromide with silver oxide yielded the silver dicarbene complexes of the type [Ag(NHC)2][AgBr2] 1–4 (NHC = picoline-functionalized benzimidazolin-2-ylidene). The silver complexes 1–4 have been used in carbene transfer reactions to yield the gold(I) complexes of the type [AuCl(NHC)] 5–8 in good yields. A halide exchange at the metal center of complexes 5–8 with lithium bromide yielded the gold bromide complexes 9–12. Finally, the oxidation of the gold(I) centers in complexes 9–12 with elemental bromine gave the gold(III) complexes of the type [AuBr3(NHC)] 13–16. Molecular structures of selected Au(I) and Au(III) complexes have been determined by X-ray diffraction studies.

Colorimetric Determination of Chloridion in Domestic Water Based on the Wavelength Shift of CsPbBr3 Perovskite Nanocrystals via Halide Exchange

Cubic phase CsPbBr3 perovskite nanocrystals (PNCs) was prepared by a high-temperature hot-injection method. The high photoluminescence quantum yield (PLQY) of as-prepared CsPbBr3 PNCs was 87%, which can be used for the determination of chloridion in domestic water samples based on their wavelength-shift characteristics via halide exchange. The proposal approach for the determination of chloridion reveals a linear correlation ranged from 10 to 200 μM of the chloridion concentration and the wavelength shift of CsPbBr3 PNCs with a correlation coefficient of R2 = 0.9956. The as-mentioned method reveals neglectable responses towards those co-existing ions in the water aside from chloridion, due to the quick exchange between Cl and Br and the outstanding color change caused by wavelength shift. The strategy has been applied to the determination of chloridion in water samples with the recoveries of 98.9–104.2% and the limit of detection (LOD) of 4 μM. These results show that the suggested approach is promising for the development of novel fluorescence detection for chloridion in water.