3 years ago

Electronic Nature of New Ir(III) Complexes: Linear Spectroscopic and Nonlinear Optical Properties

Electronic Nature of New Ir(III) Complexes: Linear Spectroscopic and Nonlinear Optical Properties
Peng Zhao, Mykhailo V. Bondar, Jianmin Shi, David J. Hagan, Salimeh Tofighi, Peter Y. Zavalij, Eric W. Van Stryland, Ryan M. O’Donnell
Comprehensive investigations of the linear and nonlinear optical properties of new Ir(III) complexes [Ir(pbt)2(dbm)] (1), [Ir(pbt)2(dmac)] (2), and [Ir(pbt)2(minc)] (3) (pbt = 2-phenylbenzothiazole; dbm = dibenzoyl methane; dmac = (1E,4Z,6E)-1,7-bis(4-(dimethylamino)phenyl)-5-hydroxyhepta-1,4,6-trien-3-one; minc = (1E,4Z,6E)-5-hydroxy-1,7-bis(1-methyl-1H-indol-3-yl)hepta-1,4,6-trien-3-one) are reported, including photostability, two-photon absorption, and femtosecond transient absorption spectroscopy. The steady-state and time-resolved spectral properties of 13 revealed the electronic nature of the absorption bands, and photoluminescence emission of 2 and 3 shows both fluorescence and phosphorescence processes occurring simultaneously in liquid solution at room temperature. This unusual behavior of 2 and 3 can be explained by a dual-minimum potential surface of the excited electronic state resulting in two independent fluorescence and phosphorescence emission channels. The degenerate 2PA spectra of 13 were obtained by open aperture Z-scans with a femtosecond laser, and maxima values of 2PA cross sections up to ∼350 GM were observed. Ultrafast relaxation processes of 13 were investigated by femtosecond transient absorption, and the characteristic times for triplet formation were determined to be <500 fs for 1 and ∼2 ps for 2 and 3 in a nonpolar medium.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcc.7b06254

DOI: 10.1021/acs.jpcc.7b06254

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