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Complex [Ag(IPr)( 3-Me dpa)][PF 6 ] (1), possessing the same combination of ligands as previously reported [Cu(IPr)( 3-Me dpa)][PF 6 ] (2) applied in a blue-emitting light-emitting electrochemical cell (LEC), has been synthesized and fully structurally and photophysically characterized both in powder and thin-film form. In detail, temperature-dependent steady-state, time-resolved emission experiments, and computational calculations have been performed to understand the impact of the nature of the metal ion center on the photophysical and electroluminescent properties. Here, a direct comparison between the complexes reveals (i) a distinct emission behavior, such as fluorescence (1) vs . thermally activated delay fluorescence (2), caused by the changes of the nature of the emitting excited states from ligand centered (1) to metal-to-ligand charge transfer (2), (ii) an unforeseen crystallinity-dependent emission in 1 that leads to either smooth and non-emissive thin-films or phase aggregated and emissive thin-films, and (iii) 1-based LECs with a stable electrical behavior over 100 h, which contrasts with the prior start-of-the-art value of a few minutes (2).

Here we report an iron-complex-catalyzed synthesis of various mono- and di-substituted quinolin-2(1 H )-ones achieved via the intramolecular acceptorless dehydrogenative cyclization of amido-alcohols. This approach for the synthesis of N-heterocycles has provided access to underdescribed disubstituted quinolinones and represents an alternative to the well-known palladium-catalyzed coupling reactions.

Heteroleptic silver(I) complexes have recently started to attract attention in thin-film lighting technologies as an alternative to copper(I) analogues due to the lack of flattening distortion upon excitation. However, the interpretation of their photophysical behavior is challenging going from traditional fluorescence/phosphorescence to a temperature-dependent dual emission mechanism and ligand-lock assisted thermally activated delayed fluorescence. Herein, we unveil the photoluminescence behavior of a three-coordinated Ag(I) complex with the N-heterocyclic carbene (NHC) ligand and 2,2'-bipyridine (bpy) as the N^N ligand. In contrast to its low-emissive Cu(I) complex structural analogues, a strong greenish emission was attributed to the presence of aggregates formed by π-π intermolecular interactions as revealed by the X-ray structure and aggregation induced emission (AIE) studies in solution. In addition, the temperature-dependent time-resolved spectroscopic and computational studies demonstrated that the emission mechanism is related to a phosphorescence emission mechanism of two very close lying (Δ E = 0.08 eV) excited triplet states, exhibiting a similar delocalized nature over the bipyridine ligands. Unfortunately, this favourable AIE is lost upon forming homogeneous thin films suitable for lighting devices. Though the films showed very poor emission, the electrochemical stability under device operation conditions is remarkable compared to the prior-art, highlighting the potential of [Ag(NHC)(N^N)][X] complexes in thin-film lighting.

Regioselective phosphonation of pyridines is an interesting transformation in synthesis and medicinal chemistry. We report herein a metal-free approach enabling access to various 4-phosphonated pyridines. The method consists of simply activating the pyridine ring with a Lewis acid (BF 3 ·OEt 2 ) to facilitate the nucleophilic addition of a phosphine oxide anion. The formed sigma complex is subsequently oxidized with an organic oxidant (chloranil) to yield the desired adducts in good to excellent yields. We furthermore showed that access to C2-phosphoinated pyridines can be achieved in certain cases with strong Lewis basic phosphorus nucleophiles or with strong Lewis acidic pyridines. Both experimental and computational mechanistic investigations were undertaken and allowed us to understand the factors controlling the reactivity and selectivity of this reaction., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)