Theoretical investigation on phosphorescent platinum complexes based on two tetradentate bipyridine ligands

In this work, the geometrical, optical, and phosphorescence properties of four complexes with general formula [dRpypy—C(OCH 3 )R′—dRpypy]Pt, with Pt-1 (R = F, R′ = methyl), Pt-2 (R = F, R′ = hexyl), Pt-3 (R = methoxy, R′ = methyl) and Pt-4 (R = methoxy, R′ = hexyl), were studied using the B3PW91 and TD-B3PW91 methods. The effect of the double substitution R and R′ on the electronic properties of the four complexes has been investigated. Replacing the two fluorine atoms with the two methoxy groups modifies the shape of the UV–vis spectra and red shift the phosphorescence spectra, while the substituents on the linker R′ do not induce changes in both absorption and phosphorescence spectra. Normal modes involved in the vibronic structure were identified and analyzed using adiabatic Hessian approaches according to the Franck–Condon approximation. The computed phosphorescence wavelengths agree with the observed ones and indicate that the fluorinated complexes exhibit a bright light blue color, while the methoxy complexes display a light spring green color. Further, temperature effects on simulated phosphorescence spectra were studied.