A series of Ir(III)-D dyads based on an iridium(III) bis-terpyridine complex as a photoactive center and tertiary amines as donor groups, as well as their individual components, have been designed to generate photoinduced charge separation. Depending on the donor group, a modular approach or a "chemistry-on-the-complex" approach has been used to prepare three different Ir(III)-D dyads. A detailed photophysical study has been performed on one Ir(III)-D dyad in which a triarylamine is linked to the iridium bis-terpyridine complex with an amido-phenyl group used as a spacer. In acetonitrile at room temperature, steady-state and time-resolved methods gave evidence of a photoinduced charge-separated state Ir(-)-D(+) with a lifetime of 70 ps. This relatively short lifetime could be due to the close proximity between the negative charge, likely localized in the bridging terpyridine, and the oxidized donor group.
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http://dx.doi.org/10.1021/ic0351038 | DOI Listing |
Inorg Chem
November 2024
Department of Chemistry and Biochemistry, The University of Alabama, Tuscaloosa, Alabama 35487-0336, United States.
Dalton Trans
May 2022
Graduate School of Nanobioscience, Yokohama City University, 22-2 Seto, Kanazawa-ku, Yokohama 236-0027, Japan.
We report, for the first time, a color change originating from the shift of the halide-to-ligand charge transfer (XLCT) band of the Ir(III) bis-terpyridine complex crystal in response to the sorption/desorption of water of crystallization. Red and orange coloration reversibly takes place by heat and cool treatments, respectively. Single X-ray crystallography shows that the Ir(III) complex possesses two waters of crystallization constructing a dimer structure, = 2.
View Article and Find Full Text PDFACS Appl Bio Mater
October 2020
Department of Chemistry and Biochemistry, North Dakota State University, Fargo, North Dakota 58108-6050, United States.
Three mononuclear or dinuclear bis(terpyridine) (tpy) iridium(III) complexes bearing pyren-1-yl (pyr) group(s) were synthesized. Their photophysical properties in water and in vitro photodynamic therapy (PDT) effects toward the human lung epithelial cancer cell line A549 and the human epidermal skin cancer cell line A431 were investigated to evaluate the effects of dinuclear versus mononuclear complexes and the impact of the oligoether substituent at the ligand. All complexes possessed pyr-tpy ligand-associated charge transfer (CT)/ππ* absorption bands at 350-550 nm, with the dinuclear complex showing the much enhanced absorptivity of this band.
View Article and Find Full Text PDFACS Appl Bio Mater
July 2019
Department of Chemistry and Biochemistry, North Dakota State University, Fargo, ND 58108-6050, USA.
Six homo- or heteroleptic tricationic Ir(R-tpy)(R-tpy) complexes (-, R/R = Ph, 4'-N(CH)Ph, pyren-1-yl, or 4'-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}Ph, tpy = 2,2';6',2"-terpyridine) were synthesized and tested for photodynamic therapy (PDT) effects. The ground- and excited-state characteristics of these complexes were studied systematically spectroscopic methods and quantum chemistry calculations. All complexes possessed intraligand charge transfer (ILCT) / metal-to-ligand charge transfer (MLCT) dominated transition(s) in their low-energy absorption bands, which red-shifted with the increased electron-releasing strength of the R/R substituent.
View Article and Find Full Text PDFJ Phys Chem A
December 2014
Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, Germany.
Iridium(III) bis(terpyridine) complexes are known as excellent triplet emitters with emission lifetimes in the order of microseconds. We report the homoleptic complex [IrL2](3+) (L = 4'-(4-2,5-bis(octyloxy)-4-styrylphenyl)ethinyl)phenyl)-2,2':6',2″-terpyridine) that shows no detectable phosphorescence at room temperature but shows fluorescence. Emission spectra of [IrL2](3+) depend on the excitation wavelength.
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