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Isomerization Reaction of Mer- To fac-Tris(2-phenylpyridinato-N,C2')Iridium(III) Monitored by Using Surface-Enhanced Raman Spectroscopy

Isomerization Reaction of Mer- To fac-Tris(2-phenylpyridinato-N,C2')Iridium(III) Monitored by Using Surface-Enhanced Raman Spectroscopy

Bo-Han Wu, Min-Jie Huang, Cheng-Chang Lai, Chien-Hong Cheng, I-Chia Chen

Inorg Chem. 2018 Apr 16;57(8):4448-4455.

PMID: 29600849

Abstract:

We developed a new method by enclosing the complex tris(2-phenylpyridinato-N,C2')Iridium(III), Ir(ppy)3 with surfactant cetyltrimethylammonium bromide (CATB), coated with a thin layer of silica then bonded to the surface of silver nanoparticle. These samples were used to acquire surface-enhanced Raman scattering (SERS) spectra. The thickness of silica layer was controlled to have efficient phosphorescence quenching and Raman enhancement by metal nanoparticle. The SERS spectra of fac- and mer-Ir(ppy)3, recorded at 633 nm excitation, display distinct ring breathing mode features because the total symmetric vibrational bands were enhanced. This provides a convenient means to differentiate these isomers with great sensitivity and to study their isomerization process. A direct conversion reaction of mer- to fac- isomerization is identified with time constant 3.1 min when mer was irradiated with Xe light. Via thermal activation, under moderate conditions (pH 5.5 and 343 K), we observed an intermediate particularly with new bands 320/662 cm-1 after heating for 17.5 h, and then those bands disappeared to form fac-Ir(ppy)3. On the basis of DFT calculations, the intermediate is proposed to contain octahedral N-N Ir(ppy)3-HO-silica structure; band at 320 cm-1 is assigned to iridium oxygen stretching mode νIr-O of this intermediate. Under acidic conditions, pH 1-2 catalyzed by silanol in silica, byproduct with band at 353 cm-1 was observed. According to the SERS bands and the calculation, this byproduct is assigned to be iridium(III) siloxide, and the new band is assigned to νIr-O.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP94928866	Tris[2-phenylpyridinato-C2,N]iridium(III)		94928-86-6	Price

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