Heteroleptic Cyclometalated Iridium(III) Complexes Displaying Blue Phosphorescence in Solution and Solid State at Room Temperature

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

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Author(s)

  • Cheng-Han Yang
  • Shih-Wen Li
  • Yi-Ming Cheng
  • Yu-Shan Yeh
  • Pi-Tai Chou
  • Gene-Hsiang Lee
  • Chih-Hsiang Wang
  • Ching-Fong Shu

Detail(s)

Original languageEnglish
Pages (from-to)7770-7780
Journal / PublicationInorganic Chemistry
Volume44
Issue number22
Online published20 Sep 2005
Publication statusPublished - 31 Oct 2005
Externally publishedYes

Abstract

A series of heteroleptic Ir(III) metal complexes 13 bearing two N-phenyl-substituted pyrazoles and one 2-pyridyl pyrazole (or triazole) ligands were synthesized and characterized to attain highly efficient, room-temperature blue phosphorescence. The N-phenylpyrazole ligands, dfpzH = 1-(2,4- difluorophenyl)pyrazole, fpzH = 1-(4-fluorophenyl)-pyrazole, dfmpzH = 1-(2,4-difluorophenyl)-3,5-dimethylpyrazole, and fmpzH = 1-(4-fluorophenyl)-3,5- dimethylpyrazole, show a similar reaction pattern with respect to the typical cyclometalated (CN) chelate, which utilizes its orthosubstituted phenyl segment to link with the central Ir(III) atom, while the second 2-pyridylpyrazole (or triazole) ligand, namely, fppzH = 3-(trifluoromethyl)-5-(2-pyridyl)pyrazole, fptzH = 3-(trifluoromethyl)-5-(2-pyridyl)triazole, and hptzH = 3-(heptafluoropropyl)-5-(2-pyridyl)triazole, undergoes typical anionic (NN) chelation to complete the octahedral framework. X-ray structural analyses on complexes [(dfpz)2Ir(fppz)] (1a) and [(fmpz)2Ir(hptz)] (3d) were established to confirm their molecular structures. Increases of the ππ* energy gaps of the Ir(III) metal complexes were systematically achieved with two tuning strategies. One involves the substitution for one or two fluorine atoms at the N-phenyl segment or the introduction of two electron-releasing methyl substituents at the pyrazole segment of the H(CN) ligands. Alternatively, we have applied the more electron-accepting triazolate in place of the pyrazolate segment for the third (NN)H ligand. Our results, on the basis of steady-state, relaxation dynamics, and theoretical approaches, lead to a conclusion that, for complexes 1-3, the weakening of iridium metal-ligand bonding strength in the T1 state plays a crucial role for the fast radiationless deactivation. For the case of [(fmpz)2Ir(hptz)] (3d), a thermal deactivation barrier of 4.8 kcal/mol was further deduced via temperature-dependent studies. The results provide a theoretical basis for future design and synthesis of the corresponding analogues suited to blue phosphorescent emitters.

Citation Format(s)

Heteroleptic Cyclometalated Iridium(III) Complexes Displaying Blue Phosphorescence in Solution and Solid State at Room Temperature. / Yang, Cheng-Han; Li, Shih-Wen; Chi, Yun; Cheng, Yi-Ming; Yeh, Yu-Shan; Chou, Pi-Tai; Lee, Gene-Hsiang; Wang, Chih-Hsiang; Shu, Ching-Fong.

In: Inorganic Chemistry, Vol. 44, No. 22, 31.10.2005, p. 7770-7780.

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