The synthesis of new Pt(II) complexes bearing tailored cyclometalated C^N*N^C luminophores is reported along with their photophysical properties. The emission of the monomeric species can be blue shifted upon formal isosteric replacement of two C-H units by N atoms at the two cyclometalating rings. Their remarkable stability upon sublimation was demonstrated by means of scanning tunneling microscopy, which also revealed a defined self-assembly behavior leading to supramolecular arrays, showing a 3-fold symmetry in 2D-confined monolayers. The supramolecular organization is driven by van der Waals interactions of the side chains and does not depend on the nature of the luminophores, as also observed in the crystalline phases showing no significant Pt-Pt interactions in 3D. Conversely, the luminescence properties in glassy matrices at 77 K and in amorphous solids are indicative of intermolecular interactions with sizable intermetallic coupling, which was demonstrated by reproducing the emission spectra of dimeric species by means of (TD)DFT calculations. The tendency toward aggregation was also traceable by cyclic voltammetry, whereas thermogravimetric analyses confirmed their stability. Solution-processed and vacuum-deposited OLED devices showed a concentration-dependent electroluminescence that red shifts with increasing doping ratios. Due to the stability of the complexes, solution-processed and vacuum-deposited devices showed identical electroluminescence spectra. Besides favoring aggregation, introduction of two N atoms has a detrimental effect on the device performance, due to the prolonged excited-state lifetimes favoring triplet-triplet annihilation.

Here we report on a novel system based on aromatic thioethers with unique luminescence properties. Fifteen different compounds were investigated in detail on their luminescence properties using UV/Vis absorption and steady-state and time-resolved luminescence spectroscopy. Excited state lifetimes as well as quantum yields were determined, and the toxicity towards HeLa cells was investigated. Besides X-ray analyses also quantum chemical calculations were performed to gain deeper insights in the unique behavior of this facile system. The studied compounds reveal remarkable fluorescence emission ranging from 437 to 588 nm as well as phosphorescence (up to 5 μs).

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