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A critical challenge facing thermally activated delayed fluorescence (TADF) is to facilitate rapid and efficient electronic transitions while ensuring a narrow singlet-triplet energy gap (ΔEST) in a single luminophore. We present a TADF-active iptycene that clearly demonstrates that homoconjugation can be harnessed as a viable design strategy towards answering this challenge. A homoconjugated analogue of an established quinoxaline-based TADF luminophore has been produced by fusing three of these luminophores together across a shared triptycene core. Homoconjugation was confirmed by electrochemistry, and as a direct consequence of this phenomenon we observed synergistic improvements to photoluminescence quantum yield (ΦPL), radiative rate of singlet decay (kSr), delayed fluorescence lifetime (τTADF), and rate of reverse intersystem crossing (krISC), all while narrowing the ΔEST. The enhancement is rationalised with TD-DFT calculations including spin-orbit coupling (SOC). A facile synthesis, the ubiquity of the pyrazine motif in state-of-the-art TADF materials of all colours, and the extent of the overall performance enhancement leads to a great potential for generality.

Abstract: By inverting the common structural motif of thermally activated delayed fluorescence materials to a rigid donor core and multiple peripheral acceptors, reverse intersystem crossing (rISC) rates are demonstrated in an organic material that enables utilization of triplet excited states at faster rates than Ir‐based phosphorescent materials. A combination of the inverted structure and multiple donor–acceptor interactions yields up to 30 vibronically coupled singlet and triplet states within 0.2 eV that are involved in rISC. This gives a significant enhancement to the rISC rate, leading to delayed fluorescence decay times as low as 103.9 ns. This new material also has an emission quantum yield ≈1 and a very small singlet–triplet gap. This work shows that it is possible to achieve both high photoluminescence quantum yield and fast rISC in the same molecule. Green organic light‐emitting diode devices with external quantum efficiency >30% are demonstrated at 76 cd m−2. [ABSTRACT FROM AUTHOR]

A phosphate-sensitive cobalt electrode was evaluated in detecting orthophosphate ions () in ammonium lactate–acetic acid soil extracts. The dependence of the mixed potential of a cobalt electrode onconcentration was investigated through potentiometry. The mechanism of detection is based on the consumption of a surface cobalt (II) oxide layer to form (Co3(PO4)2), which leads to a concentration-dependent shift of the mixed potential. Two reference electrodes were evaluated: Ag/AgCl (3 M) KCl and a platinum (Pt) wire. A linear response was observed using both reference electrodes. However, application of a Pt wire quasireference electrode increased the linear dynamic response range of the detector from 10–103 mg L−1or 10−4–10−1 M (Ag/AgCl (3 M) KCl) to 0.1–105 mg L−1or 10−6–101 M. In addition, the response time using the Pt wire was less than 5 min compared to a minimum of 10 min using Ag/AgCl (3 M) KCl. There was close agreement between the response of the phosphate-sensitive cobalt electrode with a standard colorimetric method. As dissolved organic substances can potentially interfere with electrochemical techniques, an investigation into the use of a nonpolar resin for decolorization and removal of organic matter in soil extracts was performed and successfully used. The phosphate-sensitive cobalt electrode was found to be a fast method for the analysis of soil extracts with high sensitivity and selectivity. It has the potential to be developed into a sensor for the in situ measurement of phosphate in various environmental matrices. [ABSTRACT FROM AUTHOR]

Open-shell systems with extensive π-conjugation have fascinating properties due to their narrow bandgaps and spin interactions. In this work, we report neutral open-shell di-and polyradical conjugated materials exhibiting intriguing optical and magnetic properties. Our key design advance is the planarized geometry allowing for greater interaction between adjacent spins. This results in absorption and emission in the near infrared at 803 and 1050 nanometers, respectively, and we demonstrate a unique electronic structure where a bright zwitterionic excited state is the lowest-accessible electronic transition. Electron paramagnetic resonance spectroscopy and superconducting quantum interference device measurements reveal that our materials are open-shell singlets with different degrees of spin interactions, dynamics, and antiferromagnetic properties, which likely contributed to the formation of their emissive zwitterionic singlet excited state and near-infrared emission. In addition, our materials show reversible and stable electrochromic switching with more than 500 cycles, indicating their potential for optoelectronic and electrochemical energy storage applications. [ABSTRACT FROM AUTHOR]

Conjugated polymers are an important class of chromophores for optoelectronic devices. Understanding and controlling their excited state properties, in particular, radiative and non-radiative recombination processes are among the greatest challenges that must be overcome. We report the synthesis and characterization of a molecularly encapsulated naphthalene diimide-based polymer, one of the most successfully used motifs, and explore its structural and optical properties. The molecular encapsulation enables a detailed understanding of the effect of interpolymer interactions. We reveal that the non-encapsulated analogue P(NDI-2OD-T) undergoes aggregation enhanced emission; an effect that is suppressed upon encapsulation due to an increasing π-interchain stacking distance. This suggests that decreasing π-stacking distances may be an attractive method to enhance the radiative properties of conjugated polymers in contrast to the current paradigm where it is viewed as a source of optical quenching., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

By inverting the common structural motif of thermally activated delayed fluorescence materials to a rigid donor core and multiple peripheral acceptors, reverse intersystem crossing (rISC) rates are demonstrated in an organic material that enables utilization of triplet excited states at faster rates than Ir-based phosphorescent materials. A combination of the inverted structure and multiple donor-acceptor interactions yields up to 30 vibronically coupled singlet and triplet states within 0.2 eV that are involved in rISC. This gives a significant enhancement to the rISC rate, leading to delayed fluorescence decay times as low as 103.9 ns. This new material also has an emission quantum yield ≈1 and a very small singlet-triplet gap. This work shows that it is possible to achieve both high photoluminescence quantum yield and fast rISC in the same molecule. Green organic light-emitting diode devices with external quantum efficiency >30% are demonstrated at 76 cd m -2 .