RESUMO
Low-cost molecular emitters that merge circularly polarized luminescence (CPL) and thermally activated delayed fluorescence (TADF) properties are attractive for many high-tech applications. However, the design of such emitters remains a difficult task. To address this challenge, here, we propose a simple and efficient strategy, demonstrated by the design of pseudochiral-at-metal complexes [Cu(L*)DPEPhos]PF6 bearing a (+)/(-)-menthol-derived 1,10-phenanthroline ligand (L*). These complexes exhibit a yellow CP-TADF with a record-high quantum yield (close to 100%) and high dissymmetry factor (|glum| ~ 1×10-2). Remarkably, the above compounds also show a negative thermal-quenching (NTQ) of luminescence in the 300-77 K range. Exploiting the designed Cu(I) emitters, we fabricated efficient CP-TADF OLEDs displaying mirror-imaged CPL bands with high |gEL| factors of 1.5×10-2 and the maximum EQE of 6.15%. Equally important, using the (+)-[Cu(L*)DPEPhos]PF6 complex, we have discovered that an external magnetic field noticeably suppresses CP-TADF of Cu(I) emitters. These findings are an important contribution to the CPL phenomenon and provide access to highly efficient, low-cost and robust CP-TADF emitters.
RESUMO
Multi-stimuli-responsive tetranuclear gold(I) complexes were prepared based on a tetra(alkynyl)calix[4]arene framework, with incorporation of a series of isocyanide ligands of tunable hydrophilicity. This class of complex was found to exhibit high sensitivity towards group IIIA metal ions especially In3+ . Drastic electronic absorption and emission changes were observed, which could be attributed to the formation of AuI â â â AuI interactions during the binding event. Solvent-induced self-aggregation was also observed upon changing the solvent environment to a more polar medium, with the formation of nanoaggregates and the turning-on of the aurophilic interactions, leading to interesting luminescence and morphological changes. The aggregation process was monitored by UV/Vis absorption, emission and 1 Hâ NMR spectroscopy and dynamic light scattering (DLS) studies, and the morphological changes were studied by electron microscopy. This new class of complex has shown high sensitivity towards external stimuli and demonstrated the feasibility of employing the on-off switching of aurophilicity as an effective design strategy for the construction of functional supramolecular systems.