The tetranuclear silver(I) 3,5-bis(trifluoromethyl)pyrazolate adducts with 2,2′-bipyridine derivatives were prepared by the reaction of trinuclear metal complex with the diimines. It was shown that the product structure depends on the reagents ratio: mono-and bisdiimine complexes were synthesized. Compounds obtained possess green phosphorescence in the [a] A. N. Nesmeyanov Institute of Organoelement Compounds, 4855 solid state. The short intramolecular Ag···Ag distances (≤ 3 Å) make possible electronic communication between the metal atoms which leads to the dual emissive behavior mainly due to the 3 LC phosphorescence with the impact of 3 MLCT. The behavior observed was rationalized by the TD-DFT study.by N,N-ligand. [7f ] Despite the high potential of silver pyrazolate adducts with chelating diimines to exhibit the photophysical properties the examples of such complexes are rare. [7b,7f,7i] Herein we report on the synthesis, structures and photophysical properties of a series of silver(I) 3,5-bis(trifluoromethyl) pyrazolate [3,5-(CF 3 ) 2 Pz], Pz adducts with 2,2′-bipyridine (L I ), 4,4′-dimethyl-2,2′-bipyridine (L II ) and 2,2′-biquinoline (L III ). The influence of the reagents ratio and the ligand structure on the complexation pattern, as well as the relationship between the complexes structures and their photophysical properties were studied. It was shown that the difference in the intramolecular non-covalent silver-silver interactions influences the photophysical behavior.