Syntheses, Structures and Luminescence of multinuclear Silver(I) pyrazolate adducts with 1, 10-Phenanthroline derivatives
The set of silver(I) 3,5-bis(trifluoromethyl) pyrazolate adducts with 1,10-Phenanthroline (L2), 2,9-dimethyl 1,10-phenanthroline (Neocuproine, L3) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (Bathocuproine, L4) was synthesized starting from trimeric silver pyrazolate Ag3Pz3. Reactions with sterically hindered L3 and L4 cause the destruction of the original trimeric core, yielding dinuclear Ag2Pz2 cycle of unprecedented chair configuration for L3, while bathocuproine L4 leads to the drastic rearrangement of the silver pyrazolate core into the cationic Ag(L4)2 and anionic Ag5Pz6 subunits. All complexes obtained possess the phosphorescence in the solid state. The TD-DFT calculations demonstrate the different possible emission processes explaining the emission behavior as well as the lifetimes.