Cyclometalated IrIII Complexes with Substituted 1,10‐Phenanthrolines: A New Class of Efficient Cationic Organometallic Second‐Order NLO Chromophores |
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| Authors: | Adriana Valore Dr Elena Cariati Prof?Dr Claudia Dragonetti Dr Stefania Righetto Dr Dominique Roberto Prof?Dr Renato Ugo Prof?Dr Filippo De?Angelis Dr Simona Fantacci Dr Antonio Sgamellotti Prof?Dr Alceo Macchioni Prof?Dr Daniele Zuccaccia Dr |
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| Institution: | 1. Dip. Chimica Inorganica, Metallorganica e Analitica “Lamberto Malatesta”, Università di Milano, UdR dell'INSTM di Milano and ISTM‐CNR via Venezian 21, 20133, Milano (Italy), Fax: (+39)?02‐50314405;2. ISTM‐CNR, c/o Dipartimento di Chimica, Università di Perugia via Elce di Sotto 8, 06123, Perugia (Italy), Fax: (+39)?075‐585‐5606;3. Dipartimento di Chimica, Università di Perugia via Elce di Sotto 8, 06123, Perugia (Italy), Fax: (+39)?075‐585‐5598 |
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| Abstract: | 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 benzoh]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. |
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| Keywords: | density functional calculations EFISH (electrical‐field‐ induced second‐harmonic generation) ion pairs iridium nonlinear optics |
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