DFT and TD-DFT investigation of the ground and excited states for dinuclear and mononuclear copper(I) and silver(I) complexes of 3,5-bis(trifluoromethyl)pyrazole and related bis(pyrazolyl)borate

Abstract

The ground-state and low-lying excited electronic states in mononuclear, {H 2B[3,5-(CF 3) 2Pz] 2M(2,4,6-Cn)} (M 1) and dinuclear {[3,5-(CF 3) 2Pz]M(2,4,6-Cn)} 2, (M 2) (Pz = pyrazole, Cn = collidine and M = Cu, Ag), are studied using DFT approach. Electronic properties are calculated using B3LYP, while excited singlet and triplet-states are examined using TD-B3LYP. All the calculated low-lying transitions are categorized as 1MLCT transitions. A good agreement was found between experimental spectra and predicted emission wavelengths ( λ em), the corresponding emissive states being assigned as 3MLCT for Cu 1 and Ag 2, 3MLLCT for Ag 1 and 3LLCT for Cu 2.