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• W2093075487 abstract "Tetra-peri-(tert-butyl-benzo)-di-peri-(pyrimidino)-coronene 1, the parent compound of the nitrogen heterosuperbenzene family N−HSB, is employed as a novel monotopic ligand in the formation of [Pd(η3-C3H5)(1)]PF6 2 and [Ru(bpy)2(1)](PF6)2 (where bpy = 2,2‘-bipyridine 3a and d8-2,2‘-bipyridine 3b). These N-coordinated complexes are fully characterized by 1H NMR and IR spectroscopy and ESI-MS. Metal coordination has a profound effect on both the absorption and the emission properties of 1. Pd(II) coordination causes a red-shift in the low-energy absorptions, a decrease in the intensity of the n−π* absorptions, and a quenching of the emission. Ru(II) coordination causes absorption throughout the visible region and creates two new complexes that join an elite group of compounds known as “black” absorbers. 3a and 3b possess two discernible 1MLCT bands. The one of exceptionally low energy (λmax = 615 nm) has an associated 3MLCT emission (λmax = 880 nm) due to the unprecedented electron delocalization and acceptor properties of the rigid aromatic N−HSB 1. Both Ru(II) complexes are near-IR emitters with unusually protracted emission lifetimes of 320 ns at 77 K. They are photochemically inert, and their electrochemical properties are consistent with the presence of a low-lying π* orbital on 1. The first two reversible reductions (E1/2 (CH3CN), −0.54 V, −1.01 V vs SCE) are due to the stepwise reduction of 1 and are anodically shifted as compared to [Ru(bpy)3]2+. Temperature- and concentration-dependent NMR studies on 2 and 3a suggest extensive aggregation is occurring in solution." @default.
• W2093075487 created "2016-06-24" @default.
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• W2093075487 date "2004-06-22" @default.
• W2093075487 modified "2023-10-02" @default.
• W2093075487 title "Complexed Nitrogen Heterosuperbenzene: The Coordinating Properties of a Remarkable Ligand" @default.
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• W2093075487 doi "https://doi.org/10.1021/ja0491634" @default.
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