Toward Luminescence Vapochromism of Tetranuclear AuI鈥揅uI Clusters

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• 作者：Julia R. Shakirova ; Elena V. Grachova ; Alexei S. Melnikov ; Vladislav V. Gurzhiy ; Sergey P. Tunik ; Matti Haukka ; Tapani A. Pakkanen ; Igor O. Koshevoy
• 刊名：Organometallics
• 出版年：2013
• 出版时间：August 12, 2013
• 年：2013
• 卷：32
• 期：15
• 页码：4061-4069
• 全文大小：387K
• 年卷期：v.32,no.15(August 12, 2013)
• ISSN：1520-6041

文摘

A family of triphosphine gold鈥揷opper clusters bearing aliphatic and hydroxyaliphatic alkynyl ligands of general formula [HC(PPh₂)₃Au₃Cu(C₂R)₃]⁺ (R = cyclohexyl (1), cyclopentyl (2), Bu^t (3), cyclohexanolyl (4), cyclopentanolyl (5), 2,6-dimethylheptanolyl (6), 2-methylbutanolyl (7), diphenylmethanolyl (8)) was synthesized via a self-assembly protocol, which involves treatment of the (AuC₂R)_n acetylides with the (PPh₂)₃CH ligand in the presence of Cu⁺ ions and NEt₃. Addition of Cl^{鈥?/sup> or Br鈥?/sup> anions to complex 8 results in coordination of the halides to the copper atoms to give neutral HC(PPh₂)₃Au₃CuHal(C₂COHPh₂)₃ derivatives (Hal = Cl (9), Br (10)). The title compounds were characterized by NMR and ESI-MS spectroscopy, and the structures of 1, 4, 7, and 8 were determined by single-crystal X-ray diffraction analysis. The photophysical behavior of all of the complexes has been studied to reveal moderate to weak phosphorescence in solution and intense emission in the solid state with a maximum quantum yield of 80%. Exposure of the solvent-free X-ray amorphous samples 8鈥?b>10 (R = diphenylmethanolyl) to vapors of the polar solvents (methanol, THF, acetone) switches luminescence with a visible hypsochromic shift of emission of 50鈥?0 nm. The vapochromism observed is tentatively ascribed to the formation of a structurally ordered phase upon absorption of organic molecules by the amorphous solids.}