Cyclometalated Ir(III) complexes with substituted 1,10-phenanthrolines: a new class of efficient cationic organometallic second-order NLO chromophores.
ABSTRACT Cyclometalated cationic Ir(III) 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=NO(2), H, Me, NMe(2); Y(-)=PF(6) (-), C(12)H(25)SO(3) (-), 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 Ir(III), acting as a donor push system, to pi* orbitals of the phenanthroline, acting as an acceptor pull system. Substitution of cyclometalated 2-phenylpyridine by the more pi 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 mubeta 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 NO(2) group. By using a combined experimental (the EFISH technique and (1)H and (19)F 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 mubeta values of these cationic NLO chromophores. In CH(2)Cl(2), concentration-dependent high absolute values of mubeta are obtained for [Ir(ppy)(2)(5-NO(2)-1,10-phen)]Y if Y is a weakly interacting anion, such as PF(6) (-), whereas with a counterion, such as C(12)H(25)SO(3) (-) or I(-), which form tight ion-pairs, the absolute value of mubeta is lower and quite independent of the concentration. This mubeta trend is partially due to the perturbation of the counterion on the LUMO pi* levels of the phenanthroline. The correlation between the mubeta value and dilution shows that the effect of concentration is a factor that must be taken into careful consideration.