Highly fluorescent aryl-cyclopentadienyl ligands and their tetra-nuclear mixed metallic potassium–dysprosium clusters

摘要

Two alkyl substituted triaryl-cyclopentadienyl ligands [4,4′-(4-phenylcyclopenta-1,3-diene-1,2-diyl)bis(methylbenzene) ( 1 ) and 4,4′,4′′-(cyclopenta-1,3-diene-1,2,4-triyl)tris(methylbenzene) ( 2 )] have been synthesized via cross-aldol condensation followed by Zn-dust mediated cyclization and acid catalyzed dehydration reactions. The fluorescence properties of 1 and 2 have been studied in solution and solid state. The ligands exhibited aggregation-induced emission enhancement (AIEE) in THF/water solution. 1 and 2 have been found to be significantly more fluorescent in the solid state than in their respective solutions. This phenomenon can be attributed to the strong intermolecular CH?π interactions present in 1 and 2 which leads to the tight packing of molecules in their solid-state. Both 1 , 2 and their corresponding anions have been studied by theoretical calculations. Ligands 1 and 2 have been shown to react with anhydrous DyCl _(3) in the presence of potassium metal at high temperature to afford two fluorescent chloride-bridged tetra-nuclear mixed potassium–dysprosium metallocenes [(Me _(2) Cp) _(4) Dy _(2) ~(III) Cl _(4) K _(2) ]·3.5(C _(7) H _(8) ) ( 5 ) and [(Me _(3) Cp) _(4) Dy _(2) ~(III) Cl _(4) K _(2) ]·3(C _(7) H _(8) ) ( 6 ), respectively in good yields.