New Series of Ruthenium(II) and Osmium(II) Complexes Showing Solid-State Phosphorescence in Far-Visible and Near-Infrared

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Author(s)

  • Jing-Lin Chen
  • Kellen Chen
  • Yi-Ming Cheng
  • Min-Wen Chung
  • Ya-Chien Yu
  • Gene-Hsiang Lee
  • Pi-Tai Chou
  • Ching-Fong Shu

Detail(s)

Original languageEnglish
Pages (from-to)823-832
Journal / PublicationInorganic Chemistry
Volume49
Issue number3
Online published23 Dec 2009
Publication statusPublished - 1 Feb 2010
Externally publishedYes

Abstract

A new RuII complex, [Ru(fpbpymH)2]Cl2 (1), in which fpbpymH = [5-(trifluoromethyl)pyrazol-3-yl](2,2'-bipyrid-6-yl)methane, was prepared by the treatment of [Ru(DMSO)4Cl2] with 2 equiv of the terdentate chelate fpbpymH in refluxing ethanol. A single-crystal X-ray diffraction study of 1 revealed a distorted octahedral RuII framework, showing strong N-H- ... Cl hydrogen bonding between the fpbpymH ligand and Cl anions. In the presence of Na2CO3, the methylene linkers of chelates in 1 underwent stepwise oxygenation, forming the charge-neutral complexes [Ru(fpbpym)(fpbpyk)] (2) and [Ru(fpbpyk)2] (3) [fpbpykH = [5-(trtfluoromethyl)pyrazol-3-yG(2,2'-bipyrid-6-yl) ketone] in sequence. The respective charge-neutral OsII complex [Os(fpbpyk)2] (4) was also isolated by the treatment of OsCl3·3H2O with 2 equiv of the terdentate chelate fpbpymH. Electrochemical analysis indicated that the introduction of the electron-withdrawing ketone group in 2-4 increased the metal-based oxidation potential in sequence. For the photophysical properties, complexes 1-4 are essentially nonluminescent in solution (e.g., CH2Cl2 or MeOH) at room temperature, but all exhibit 600-1100 nm phosphorescence with moderate intensity for the powdery, solid sample at room temperature. The trend in terms of the emission peak wavelength of 1 (666 nm) < 3 (795 nm) < 2 (810 nm) < 4 (994 nm) among titled complexes is in agreement with the corresponding onset of absorption spectra as well as the time-dependent density functional theory calculation of 1 < 3 < 2 < 4.

Citation Format(s)

New Series of Ruthenium(II) and Osmium(II) Complexes Showing Solid-State Phosphorescence in Far-Visible and Near-Infrared. / Chen, Jing-Lin; Chi, Yun; Chen, Kellen; Cheng, Yi-Ming; Chung, Min-Wen; Yu, Ya-Chien; Lee, Gene-Hsiang; Chou, Pi-Tai; Shu, Ching-Fong.

In: Inorganic Chemistry, Vol. 49, No. 3, 01.02.2010, p. 823-832.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review