Photoelectric properties of novel amide-functionalized Ir(III) complexes

Wei Shen, Wen Wen Tian, Zheng Jian Qi, Yue Ming Sun

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Abstract

A series of luminescent cyclometalated Ir(III) complexes functionalized with amide derivatives were prepared and compared with [Ir(ppy)2phen-NH2]Cl. The complexes were [Ir(ppy)2phen-Br]Cl, [Ir(ppy)2phen-COOH]Cl, and [Ir(ppy)2phen-Si]Cl, where ppy is 2-phenylpyridine, phen-NH2 is 5-amino-[1,10]-phenanthroline, phen-Br is 2-bromo-2-methyl-N-(1,10-phenanthrolin-5-yl)propanamide, phen-COOH is 4-[(1,10-phenanthrolin-5-yl)amino]-4-oxobut-2-enoic acid, and phen-Si is 5-[N,N-bis-3-(triethoxysilyl) propyl]ureyl-1,10-phenanthroline. They were characterized using nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), ultraviolet-visible (UV-Vis) absorption spectroscopy, photoluminescence (PL) spectroscopy, and cyclic voltammetry (CV). The three novel complexes have intense absorptions in the blue-purple region. The complexes show bright yellow to orange PL emissions under UV irradiation, and the quantum yields (Φ) of these complexes are higher than 12%. The excited-state lifetimes of the novel complexes are 9.18–12.00 μs, much longer than that of [Ir(ppy)2phen-NH2]Cl (5.78 μs). With both the highest quantum yield (32%) and longest lifetime (12.00 μs), [Ir(ppy)2phen-Br]Cl also shows the best oxygen-sensing properties and the largest I0/I factor, 10.91 (I0: the PL intensity of the complex in the absence of O2, I: the PL intensity of the complex under pure oxygen). These results suggest that [Ir(ppy)2phen-Br]Cl may be a promising candidate for use in oxygen sensors based on covalent grafting. Time-dependent density functional theory (TD-DFT) calculations were used to supplement the photoelectric property studies. Theoretical calculations indicate that all the mononuclear complexes have approximately octahedral structures with Ir(III) as the coordination center. The computational results agree well with the experimental data.

Original languageEnglish
Pages (from-to)2174-2182
Number of pages9
JournalActa Physico - Chimica Sinica
Volume31
Issue number11
DOIs
Publication statusPublished - 13 Nov 2015
Externally publishedYes

Keywords

  • Ir(III) complex
  • Luminescence sensor
  • Oxygen quenching
  • Phenanthroline
  • Photoelectric property

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