Cyclometalated IrIII Complexes with Substituted 1,10-Phenanthrolines: A New Class of Efficient Cationic Organometallic Second-Order NLO Chromophores

摘要

Cyclometalated cationic IrIII complexes with substituted 1,10-phenanthrolines (1,10-phen), such as [Ir(ppy)₂(5-R-1,10-phen)]Y (ppy=cyclometalated 2-phenylpyridine; R=NO₂, H, Me, NMe₂; Y−=PF₆−, C₁₂H₂₅SO₃−, I−) and [Ir(ppy)₂(4-R,7-R-1,10-phen)]Y (R=Me, Ph) are characterized by a significant second-order optical non linearity (measured by the electrical field induced second harmonic generation (EFISH) technique). This nonlinearity is controlled by MLCT processes from the cyclometalated IrIII, acting as a donor push system, to π* orbitals of the phenanthroline, acting as an acceptor pull system. Substitution of cyclometalated 2-phenylpyridine by the more π delocalized 2-phenylquinoline (pq) or benzo[h]quinoline (bzq) or by the sulfur-containing 4,5-diphenyl-2-methyl-thiazole (dpmf) does not significantly affect the μβ absolute value, which instead is affected by the nature of the R substituents on the phenanthroline, the higher value being associated with the electron-withdrawing NO₂ group. By using a combined experimental (the EFISH technique and 1H and 19F PGSE NMR spectroscopy) and theoretical (DFT, time-dependent-DFT (TDDFT), sum over states (SOS) approach) investigation, evidence is obtained that ion pairing, which is controlled by the nature of the counterion and by the concentration, may significantly affect the μβ values of these cationic NLO chromophores. In CH₂Cl₂, concentration-dependent high absolute values of μβ are obtained for [Ir(ppy)₂(5-NO₂-1,10-phen)]Y if Y is a weakly interacting anion, such as PF₆−, whereas with a counterion, such as C₁₂H₂₅SO₃− or I−, which form tight ion-pairs, the absolute value of μβ is lower and quite independent of the concentration. This μβ trend is partially due to the perturbation of the counterion on the LUMO π* levels of the phenanthroline. The correlation between the μβ value and dilution shows that the effect of concentration is a factor that must be taken into careful consideration.