Theoretical Study and Design of Phosphorescent Cyclometalated (C^∧C*)Pt^II(acac) Complexes: The Substituent Effect...

Density functional theory (DFT) and time-dependent DFT calculations were performed to evaluate the influence of substituent effect of (1) R = 4-Me, (2) R = 4-OMe, and (3) R = 2,3-OC₆H₄ on the phenyl ring of (C^∧C*)Pt^II(acac) (C^∧C* = phenylimidazole, acac = acetylacetone), respectively, on absorption and phosphorescent spectra properties, as well as the radiative and nonradiative processes. We found that emissions of complexes 2 and 3 originate from the Kasha-like T₁ state, whereas that of complex 1 originates from non-Kasha T₂ state. Compared with the emission of complex 1, the emission peaks of 2 and 3 are red-shifted, which is attributed to p-π and π-π conjugation effects resulting from the electron-donating groups -OCH₃ and -OC₆H₄ with ligand C^∧C*, respectively. The radiative rate constants (κ_r) of 2 and 3 are larger than that of 1, namely, κ_r(1) < κ_r(2) < κ_r(3), indicating that κ_r can be efficiently increased by enlarging π-conjugation at the main ligand of (C^∧C*)Pt^II(acac), which can cause the increase of spin-orbit coupling (SOC) matrix elements. At the same time, the activation energy barriers for the rate-limiting step can be largely raised accompanied by enlarging the ability of electron-donation of the substituent group at the main ligand of (C^∧C*)Pt^II(acac), which can cause the decrease of the nonradiative rate constant (κ_nr), namely, κ_nr(1) > κ_nr(2) > κ_nr(3). According to Φ_P = κ_r/(κ_r + κ_nr), the quantum yields should have the sequence Φ_P(1) < Φ_P(2) < Φ_P(3), which is in accordance with the experiment. In addition, to guide experimental synthesis of highly efficient (C^∧C*)Pt^II(acac), a new complex 4 through extending the π-conjugation in the C^∧C* ligand of (C^∧C*)Pt^II(acac) was theoretically designed, which has a larger quantum yield than 1-3.