- Giant Concentric Metallosupramolecule with Aggregation-Induced Phosphorescent Emission
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Fluorescent metallosupramolecules have received considerable attention due to their precisely controlled dimensions as well as the tunable photophysical and photochemical properties. However, phosphorescent analogues are still rare and limited to small structures with low-temperature phosphorescence. Herein, we report the self-assembly and photophysical studies of a giant, discrete metallosupramolecular concentric hexagon functionalized with six alkynylplatinum(II) bzimpy moieties. With a size larger than 10 nm and molecular weight higher than 26000 Da, the assembled terpyridine-based supramolecule displayed phosphorescent emission at room temperature. Moreover, the supramolecule exhibited enhanced aggregation-induced phosphorescent emission compared to the ligand by tuning the aggregation states through intermolecular interactions and significant enhancement of emission to CO2 gas.
- Li, Yiming,Huo, Gui-Fei,Liu, Bingqing,Song, Bo,Zhang, Yuan,Qian, Xiaomin,Wang, Heng,Yin, Guang-Qiang,Filosa, Alexander,Sun, Wenfang,Hla, Saw Wai,Yang, Hai-Bo,Li, Xiaopeng
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- Self-assembly of dinuclear helical and nonhelical complexes with copper(I)
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The ligand 1,3-bis(1-methylbenzimidazol-2-yl)benzene (mbzimbe, L3) reacts with copper(I) to give [Cu2(L3)2](ClO4)2. The crystal structure of this compound (Cu2C44H36N8Cl2O 8, a = 13.661 (1) ?, b = 19.829 (3) ?, c = 15.413 (2) ?, orthorhombic, Pbca, Z = 4) shows a dinuclear centrosymmetrical nonhelical structure in which each copper is linearly coordinated by a benzimidazole group of each ligand. The complex displays a weak intramolecular stacking interaction between the benzene groups. This complex can be considered as a stereoconformer of the double-helical complex [Cu2(L1)2](ClO4)2 (L1; 2,6-bis(1-methylbenzimidazol-2-yl)pyridine). Conductivity measurements and UV-visible spectra show that the dimeric structures are maintained in solution in polar aprotic solvents. 1H NMR measurements show that [Cu2(L1)2]2+ retains its helical structure in solution. Comparison of helical and nonhelical structures with those formed by Cu(I) with related ligands allows discussion of the factors favoring the formation of self-assembled dinuclear complexes.
- Rüttimann, Stéphane,Piguet, Claude,Bernardinelli, Gérald,Bocquet, Bernard,Williams, Alan F.
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p. 4230 - 4237
(2007/10/02)
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