Proton sensitive charge-transfer excited states in bis-terdentate cyclometalated Ir(III) complexes: Spectroscopic and theoretical investigation

Two bis-terdentate cyclometalated Ir(III) complexes with polypyridyl (N^N^N) and cyclometalated (C^N^C) ligands [Ir-Py]+ and [Ir-Py-Me]2+ have been synthesized and characterized. Their absorption and emission properties have been examined, more particularly in MeCN as a function of the addition of different acids. Depending on the acid strength and concentration, two distinct effects have been observed. For acetic acid at high concentration or trifluoroacetic acid (TFA) at low concentration, the pyridine moiety of [Ir-Py]+ is protonated; its spectroscopic behaviour is then similar to that of [Ir-Py-Me]2+. Moreover at higher concentration in TFA, the methoxy group of both complexes is protonated. The spectroscopic and electrochemical data as well as the DFT and TD-DFT calculations support contributions of charge-transfer excited states in absorption and emission from metal-ligand/ligand based HOMOs to ligand-based LUMOs, i.e. MLLCT.SCOPUS: ar.jinfo:eu-repo/semantics/publishe

Two RuIILinkage Isomers with Distinctly Different Charge Transfer Photophysics

The ligand PHEHAT (PHEHAT = 1,10-phenanthrolino[5,6-b]1,4,5,8,9,12-hexaazatriphenylene) presents a structural asymmetry that has a dramatic influence on the photophysical properties depending on the chelation site of the metal ion in the linkage isomers. While [RuII(phen)2HATPHE]2+ behaves classically, like [RuII(bpy)3]2+, [RuII(phen)2PHEHAT]2+ exhibits an unusual behavior. It appears that this complex has two 3MLCT bright states, the lower one being weakly emissive or nonemissive depending on the solvent and temperature. Different photophysical techniques involving a wide range of various temperatures and timescales are essential to analyze this difference. A full photophysical scheme is proposed based on experimental data and density functional theory calculations. While previous studies focused on high temperatures and longer timescale emission, we explore the complexes at very low temperatures and very short times in order to obtain a more complete picture of the intriguing photophysical behavior of these complexes.SCOPUS: ar.jinfo:eu-repo/semantics/publishe