title: Synthesis and photochemical properties of pH responsive tris-cyclometalated iridium(III) complexes that contain a pyridine ring on the 2-phenylpyridine ligand.
abstract: In our previous publication, it was reported that fac-Ir(atpy)3 3 (atpy = 2-(5'-amino-4'-tolyl)pyridine), which contains three amino groups at the 5'-position of the atpy ligands, exhibits a pH-dependent change in the color of the emitted radiation. Aqueous solution of 3 shows a weak red emission (at around 613 nm) under neutral or basic conditions, but the emission color changes to green (at around 530 nm) under acidic conditions, where the NH2 group is protonated to become an electron-withdrawing (NH3)(+) group. In this manuscript, we report on the preparation of some new pH-responsive Ir(III) complexes; fac-Ir(4Pyppy)3 5 and fac-Ir(3Pyppy)3 6 that contain three pyridyl groups at the 5'-position of the 2-phenylpyridine (ppy) ligand, and Ir(4Pyppym)3 7 and Ir(3Pyppym)3 8 that contain a pyridyl group at the same position of the 2-phenylpyrimidine (ppym) ligand. The introduction of three pyridyl groups on iodinated Ir(ppy)3 and Ir(ppym)3 was achieved via Suzuki-Miyaura cross-coupling reaction assisted by microwave irradiation. Solutions of the acid-free Ir(III) complexes 5, 6, 7, and 8 showed a strong green emission (at around 500 nm) in dimethylsulfoxide (DMSO). Protonation of three pyridyl groups of 5 and 7 causes a significant red-shift in the emission wavelength (at around 600 nm) with a decrease in emission intensity. The pH-dependent emission change of these complexes is also discussed. The generation of singlet oxygen ((1)O2) by the photoirradiation of the Ir complexes 5 and 6 was evidenced by the decomposition of 1,3-diphenylisobenzofuran (DPBF), the oxidation of thioanisole, and the oxidation of 2,2,5,5-tetramethyl-3-pyrroline-3-carboxamide (TPC). The induction of necrosis-like cell death of HeLa-S3 cells upon photoirradiation of 5 at 465 nm is also reported.
authors.affiliation: Faculty of Pharmaceutical Sciences and ‡Center for Technologies against Cancer, Tokyo University of Science , 2641 Yamazaki, Noda, Chiba 278-8510, Japan.
authors.forename: Akihiro
authors.initials: A
authors.lastname: Nakagawa
authors.forename: Yosuke
authors.initials: Y
authors.lastname: Hisamatsu
authors.forename: Shinsuke
authors.initials: S
authors.lastname: Moromizato
authors.forename: Masahiro
authors.initials: M
authors.lastname: Kohno
authors.forename: Shin
authors.initials: S
authors.lastname: Aoki
mesh_terms: D000970:Antineoplastic Agents / Q000138:chemical synthesis / Q000737:chemistry / Q000494:pharmacology*; D016923:Cell Death / Q000187:drug effects; D049109:Cell Proliferation / Q000187:drug effects; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry* / Q000494:pharmacology*; D004305:Dose-Response Relationship, Drug; D004354:Drug Screening Assays, Antitumor; D006367:HeLa Cells; D006801:Humans; D006863:Hydrogen-Ion Concentration; D007495:Iridium / Q000737:chemistry*; D008024:Ligands; D008856:Microscopy, Fluorescence; D015394:Molecular Structure; D055668:Photochemical Processes; D011725:Pyridines / Q000737:chemistry*; D011789:Quantum Theory; D013329:Structure-Activity Relationship; D014407:Tumor Cells, Cultured; D014466:Ultraviolet Rays
chemical_list: D000970:Antineoplastic Agents; D056831:Coordination Complexes; D008024:Ligands; D011725:Pyridines; D007495:Iridium