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- W4251176870 abstract "Tetraaryloxy-substituted perylene tetracarboxylic acid bisimides with one or two 4-pyridyl receptor substituents at the imide functionality were synthesized and employed in transition metal directed self-assembly with PdII and PtII phosphane triflates. Upon mixing of the components, quantitative formation of functional molecular square-type complexes containing four dye molecules and model complexes of a 2:1 (perylene bisimide ligand:transition metal ion) stoichiometry was observed. The isolated metallosupramolecular squares were characterized by 1H and 31P {1H} NMR spectroscopy as well as conventional electrospray ionization (ESI) and ESI-FTICR mass spectrometry, which gave evidence for the structure and the high stability of these giant cyclic dye assemblies (molecular weight (3 a)=8172, Pt−Pt corner diagonal ca. 3.4 nm). Studies of the optical absorption and fluorescence properties and the electrochemistry and spectroelectrochemistry of both the perylene bisimide ligands and the perylene bisimide metal complexes show that PtII coordination does not interfere with the optical and electrochemical properties of the perylene bisimide ligands; this gives squares with high fluorescence quantum yields (ΦF (3 a)=0.88) and three fully reversible redox couples. The latter could be unambiguously related to quantitative formation of perylene bisimide radical cations (E1/2=+0.93 V vs. Fc/Fc+), radical anions (E1/2=−1.01 V vs. Fc/Fc+), and dianions (E1/2=−1.14 V vs. Fc/Fc+); these redox reactions change the charge state of the cyclic assembly from +12 to zero. In contrast, PdII coordination influenced the electrochemical properties of the assembly because of an irreversible palladium reduction at E1/2=−1.15 V versus Fc/Fc+. Finally, dynamic ligand exchange processes between different metallosupramolecular assemblies were investigated by multinuclear NMR and electrospray mass spectrometry. These studies confirmed the reversible nature of the pyridine−PtII/PdII coordination process." @default.
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- W4251176870 date "2001-02-16" @default.
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- W4251176870 title "Fluorescent and Electroactive Cyclic Assemblies from Perylene Tetracarboxylic Acid Bisimide Ligands and Metal Phosphane Triflates" @default.
- W4251176870 doi "https://doi.org/10.1002/1521-3765(20010216)7:4<894::aid-chem894>3.3.co;2-e" @default.
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