| Luminescent metal complexes have received extensive attention and research due to their diverse structures and broad application prospects.A large number of metal complexes have various types of luminescence,such as ligand/exciton luminescence,metal/clusterluminescence,chargetransition?ligand?metal/metal?ligand?luminescence,guest molecule induced luminescence,aggregation induced luminescence,circularly polarized luminescence,and rubbing light etc.Different organic chromophore groups can be selected,and metal ions can be self-assembled to construct functional complex luminescent materials with novel structures and adjustable properties.Pyrazole metal complexes are favored by researchers because of their simple and rapid synthesis,diverse structure and remarkable optical properties.Therefore,it is very meaningful to prepare a pyrazole metal complex having structural correlation and to study the correlation between its optical properties and structure.Based on this,we have done the following two parts in this paper.First,we prepared four similar structure but different fluorescent properties eight-nuclear zinc complexes[Zn8?OH?4?L?12].By adjusting the size of chromophore groups?benzene,naphthalene,anthracene,pyrene?,weobtained4-benzyl-3,5-dimethyl-1H-pyrazole?L1?,3,5-dimethyl-4-?naphthalene-2-ylmethyl?-1H-pyrazole?L2?,3,5-dimethyl-4-?anthracen-9-ylmethyl?-1H-pyrazole?L3?and3,5-dimethyl-4-?pyren-1-ylmethyl?-1H-pyrazole?L4?.And these ligands respectively reacted with zinc ions to afford four octagonal zinc complexes with the same core but differentprotectingligands,namely,[Zn8?OH?4?L1?12]·2THF?1?,[Zn8?OH?4?L2?12]·THF?2?,[Zn8?OH?4?L3?12]·4THF?3?,[Zn8?OH?4?L4?12]·THF?4?.The structures of this series of Zn-pyrazole complexes were determined by single crystal X-ray diffraction.Based on the stable core of the eight-nuclear zinc skeleton,we can study its optical properties in depth,and the complexes 1-4 exhibit different fluorescent properties.In particular,Complex 2 exhibits white luminescence under UV light at room temperature,with a CIE coordinates?0.32,0.35?,which shows a second-scale afterglow at low temperature.Second,under an alkaline condition,we successfully synthesized a series of prominentAIEactivecoinagemetalcomplexes,namely([Au3?DTBP?3]?CH2Cl2?CHCl3?5?,[Ag3?DTBP?3]?2CHCl3?6??[Cu3?DTBP?3]?2CHCl3?7?,by reacting 3,5-dimethyl-4-?4-?1,2,2-triphenylvinyl?benzyl?-1H-pyrazole?DTBP?with coinage metal ions in the presence of triethylamine.All of these complexes have been successfully elucidated by X-ray crystallography.It was found that these complexes exhibited excellent solvent-induced aggregation-induced luminescence?AIE?performance,and their quantum yield?QY?was significantly improved compared to organic ligands?quantum yield of complex 6 was 12.01%,7.5 times to ligand?.And compared to the luminescence of the ligand itself,there are few coinage metal complexes with precise atomic structure and excellent solvent-induced AIE activity.Therefore,this work opens up a new way to develop metal-based AIE luminescent materials with high emission efficiency that are easy to prepare. |
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