Elucidation of an Aggregate Excited State in the Electrochemiluminescence and Chemiluminescence of a Thermally Activated Delayed Fluorescence (TADF) Emitter.

The electrochemistry, electrochemiluminescence (ECL), and chemiluminescence (CL) properties of a thermally activated delayed fluorescence (TADF) emitter 4,4'-(1,2-dihydroacenaphthylene-5,6-diyl)bis(N,N-diphenylaniline) (TPA-ace-TRZ) and three of its analogues were investigated. TPA-ace-TRZ exhibits both (a) delayed onset of ECL and (b) long-persistent luminescence, which we have attributed to the formation of an aggregate excited state in excimer or exciplex form. The evidence of this aggregate excited state was consistent across ECL annihilation and coreactant pathways as well as in CL. The absolute ECL efficiency of TPA-ace-TRZ using benzoyl peroxide (BPO) as a coreactant was found to be 0.028%, which was 9-fold stronger than the [Ru(bpy)3]2+/BPO reference coereactant system. Furthermore, the absolute CL quantum efficiency of TPA-ace-TRZ was determined to be 0.92%. The performance and flexibility of the TADF emitter TPA-ace-TRZ under these various emissive pathways are highly desirable toward applications in sensing, imaging, and light-emitting devices.

Absolute Electrochemiluminescence Efficiency Quantification Strategy Exemplified with Ru(bpy)32+ in the Annihilation Pathway.

This work presents a thorough guide to procedures for absolute electrochemiluminescence (ECL) quantum efficiency (ΦECL) measurements, which if employed effectively should raise the research impact of ECL studies for any luminophore. Absolute measurements are not currently employed in ECL research. Instead, ECL efficiencies have been determined relative to Ru(bpy)32+ under similar conditions, regardless of whether the conditions are favorable for Ru(bpy)32+ emissions or not. In fact, the most cited Ru(bpy)32+ ΦECL is from the pioneering work by the Bard research group in 1973 by means of a rotating ring-disk electrode revolving at 52 rotations per second measured with a silicon photodiode. Our presented technique uses a common disk electrode, spectrometer, and photomultiplier tube to measure the ΦECL. The more common light detection hardware and electrodes combined with an in-depth calculation walkthrough will provide ECL researchers the necessary tools to implement ΦECL measurement procedures in their own laboratories. Following a facile instrument setup and calculation, a systematic study of Ru(bpy)32+ ΦECL finds comparable results to those performed by Bard and co-workers.

Electrogenerated Chemiluminescence and Electroluminescence of N-Doped Graphene Quantum Dots Fabricated from an Electrochemical Exfoliation Process in Nitrogen-Containing Electrolytes.

Artificial lighting sources are one of the most important technological developments for our modern lives; the search for cost-effective and efficient luminophores is therefore crucial to a sustainable future. Graphene quantum dots (GQDs) are carbon-based nanomaterials that exhibit exceptional optical and electronic properties, making them a prime candidate for a luminophore in a light-emitting device. Nitrogen-doped GQDs fabricated from a facile top-down electrochemical exfoliation process with a nitrogen-containing electrolyte in this report showed strong photoluminescent emission at 450 nm, and electrogenerated chemiluminescence at 660 nm in the presence of benzoyl peroxide as a coreactant. When introduced into solid-state light-emitting electrochemical cells, for the first time, the GQDs displayed a broad white emission centered at 610 nm, corresponding to Commision Internationale de l'eclairage (CIE) colour coordinates of (0.38, 0.36).

Film Electrochemiluminescence Controlled by Interfacial Reactions Along with Aggregation-, Matrix-Coordination-, and Crystallization-Induced Emissions.

The utility of electrochemiluminescence (ECL) in analysis has been proven by its use in the interrogation of novel luminophores as well as the commercial applications of immunoassays. This Minireview discusses the recent advances in film ECL enhancements controlled by interfacial reactions along with aggregation-induced, crystallization-induced, matrix-coordination-induced and nanoparticle surface state emissions. These enhancement phenomena are anticipated to lead to applications toward biological and medical diagnosis. Interfacial ECL enhancements of nanoparticle films and an in-depth analysis of the application of this knowledge into development of optoelectronics follow. Finally, recent novel crystallization induced ECL enhancements and hypochromic shifts are provided. Future analyses of these film ECL enhancement phenomena will provide complementary information for the optimal implementation of next generation luminophores into thin film optoelectronic and sensing applications.