Nanocluster Transformation Induced by SbF6- Anions toward Boosting Photochemical Activities.

The interactions between SbF6- and metal nanoclusters are of significance for customizing clusters from both structure and property aspects; however, the whole-segment monitoring of this customization remains challenging. In this work, by controlling the amount of introduced SbF6- anions, the step-by-step nanocluster evolutions from [Pt1Ag28(S-Adm)18(PPh3)4]Cl2 (Pt1Ag28-Cl) to [Pt1Ag28(S-Adm)18(PPh3)4](SbF6)2 (Pt1Ag28-SbF6) and then to [Pt1Ag30Cl1(S-Adm)18(PPh3)3](SbF6)3 (Pt1Ag30-SbF6) have been mapped out with X-ray crystallography, with which atomic-level SbF6- counterion effects in reconstructing and rearranging nanoclusters are determined. The structure-dependent optical properties, including optical absorption, photoluminescence, and electrochemiluminescence (ECL), of these nanoclusters are then explored. Notably, the Pt1Ag30-SbF6 nanocluster was ultrabright with a high phosphorescence quantum yield of 85% in N2-purged solutions, while Pt1Ag28 nanoclusters were fluorescent with weaker emission intensities. Furthermore, Pt1Ag30-SbF6 displayed superior ECL efficiency over Pt1Ag28-SbF6, which was rationalized by its increased effectively exposed reactive facets. Both Pt1Ag30-SbF6 and Pt1Ag28-SbF6 demonstrated unprecedented high absolute ECL quantum efficiencies at sub-micromolar concentrations. This work is of great significance for revealing the SbF6- counterion effects on the control of both structures and luminescent properties.

Analyzing Near-Infrared Electrochemiluminescence of Graphene Quantum Dots in Aqueous Media.

Mechanisms of emissions, especially electrochemiluminescence (ECL), for graphene quantum dots (GQDs) are poorly understood, which makes near-infrared (NIR)-emitting GQDs difficult to create. To explore this poorly understood NIR ECL, two GQDs, nitrogen-doped GQDs (GQD-1) and nitrogen- and sulfur-doped ones (GQD-2), were prepared by a simple one-step solvothermal reaction with similar core structures but different surface states. The GQDs were analyzed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. Photoluminescence results, with a comparable quantum efficiency of 13% to strong luminophores in aqueous media, suggested a mechanism that the emission mainly depends on the core structure while slightly adjusted by the heteroatom doping. ECL of GQD-2 dispersed in aqueous media with K2S2O8 as the coreactant was measured by means of ECL-voltage curves and ECL spectroscopy, demonstrating strong NIR emissions between 680 and 870 nm, with a high ECL efficiency of 13% relative to that of the Ru(bpy)32+/K2S2O8 system. Interestingly, ECL is generated by surface excited states emitting light at a much longer wavelength in the NIR region. The easily prepared GQD-2 has several advantages such as low cost and quite strong NIR-ECL in aqueous media, with which wide applications in biodetection are anticipated.

Electrochemiluminescence and Photoluminescence of Carbon Quantum Dots Controlled by Aggregation-Induced Emission, Aggregation-Caused Quenching, and Interfacial Reactions.

Carbon quantum dots (CQDs) show promise in optoelectronics as a light emitter due to simple synthesis, biocompatibility and strong tunable light emissions. However, CQDs commonly suffer from aggregation caused quenching (ACQ), inhibiting the full potential of these light emitters. Studies into different ideal light emitters have shown enhancements when converting common ACQ effects to aggregation induced emission (AIE) effects. We report CQD synthesis using citric acid and high/low thiourea concentrations, or sample 2/1. These two CQDs exhibited AIE and ACQ PL effects, respectively. CQD characterizations and photoluminescence interrogations of CQD films and solutions revealed that these unique emission mechanisms likely arose from different S incorporations into the CQDs. Furthermore, it was discovered that sample 2 emitted electrochemiluminescence (ECL) more intensely than sample 1 in a homogenous solution with S2O82- as a coreactant, due to aggregation and interactions of CQD species in solution. Very interestingly, sample 1's CQD film|S2O82- system achieved an ECL efficiency of 26% and emitted roughly 26 times more efficiently than sample 2 in the same conditions. Predominant interfacial reactions and surface state emission produced intense white light with a correlated color temperature of 2000 K. Spooling ECL spectroscopy was utilized to investigate emission mechanisms. Sample 2's CQD film|TPrA system had four times higher ECL intensity than that of sample 1, most likely due to π-cation interactions leading to a strong CQD•+ stability, thereby, enhancing ECL. It is anticipated that ECL enhancement of CQD films or solutions by means of AIE will lead to wide CQD optoelectronic applications.

Efficient White Electrochemiluminescent Emission From Carbon Quantum Dot Films.

Carbon quantum dots (CQDs) were manufactured from citric acid and urea in a gram-scale synthesis with a controlled size range between 1. 5 and 23.8 nm. The size control was realized by varying volume of the precursor solution in a hydrothermal synthesis method. The prepared CQDs were investigated using electrochemiluminescence (ECL) spectroscopy at interfaces of their electrode films and electrolyte solution containing coreactants rather than conventional optoelectronic tests, providing an in-depth analysis of light-emission mechanisms of the so-called half-cells. ECL from the CQD films with TPrA and K2S2O8 as coreactants provided information on the stability of the CQD radicals in the films. It was discovered that CQD•- has a powerful electron donating nature to sulfate radical to generate ECL at a relative efficiency of 96% to the Ru(bpy)3Cl2/K2S2O8 coreactant system, indicating a strong performance in light emitting applications. The smaller the CQD particle sizes, the higher the ECL efficiency of the film interface, most likely due to the increased presence of surface states per mass of CQDs. Spooling ECL spectroscopy of the system revealed a potential-dependent light emission starting from a deep red color to blue-shifted intensity maximum, cool bright white emission with a correlated color temperature of 3,200 K. This color temperature is appropriate for most indoor lighting applications. The above ECL results provide information on the performance of CQD light emitters in films, permitting preliminary screening for light emitting candidates in optoelectronic applications. This screening has revealed CQD films as a powerful and cost-effective light emitting layer toward lighting devices for indoor applications.

Facile synthesis and efficient electrochemiluminescence of a readily accessible pyridopyrimidine.

Through a facile one-pot three-component reaction and a subsequent acetylation strategy, a novel greenish-blue fluorescent 4-imino-4H-pyrido[1,2-a]pyrimidine-3-carbonitrile (IPPC) was synthesized. Electrochemiluminescence (ECL) of IPPC was firstly found to produce efficient emission at 500 nm with reducing coreactants. Its very similar ECL and PL spectra suggest that ECL production is mainly from the monomeric excited states.