Facile synthesis and characterization of phosphorescent Pt(N ^C^N)X complexes

Zixing Wang, Eric Turner, Vanessa Mahoney, Sijesh Madakuni, Thomas Groy, Jian Li

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Abstract

In order to investigate the ground state and excited state properties of Pt(N^C^N)X, we have prepared a series of Pt complexes, where N^C^N aromatic chelates are derivatives of m-di(2-pyridinyl)benzene (dpb) and X are monoanionic and monodentate ancillary ligands including halide and phenoxide. Facile synthesis of platinum m-di(2-pyridinyl)benzene chloride and its derivatives, using controlled microwave heating, was reported. This method not only shortened the reaction time but also improved the reaction yield for most of the Pt complexes. Two Pt(N^C^N)X complexes have been structurally characterized by X-ray crystallography. The change of functional group does not affect the structure of the core Pt(N^C^N)Cl fragment. Both molecules pack as head-to-tail dimers, each molecule of the dimer related to the other by a center of inversion. The electrochemical studies of all Pt complexes demonstrate that the oxidation process occurs on the metal-phenyl fragment and the reduction process is associated with the electron accepting groups like pyridinyl groups and their derivatives. The maximum emission wavelength of the Pt(N^C^N)X complexes ranges between 471 and 610 nm, crossing the spectrum of visible light. Most of the Pt complexes are strongly luminescent (Φ = 0.32-0.63) and have short luminescence lifetimes (τ = 4-7 μs) at room temperature. The lowest excited state of the Pt(N ^C^N)X complexes is identified as a dominant ligand-centered 3π-π* state with some 1MLCT/3MLCT character, which appears to have a larger 1MLCT component than their bidentate and tridentate analogs. This results in a high radiative decay rate and high quantum yield for Pt(dpb)Cl and its analogs. However, the excited state properties of the Pt(N^C ^N)X complexes are strongly dependent on the nature of the electron-accepting groups and substituents to the metal-phenyl fragment. A rational design will be needed to tune the emission energies of the Pt(N ^C^N)X complexes over a wide range while maintaining their high luminescent efficiency.

Original languageEnglish (US)
Pages (from-to)11276-11286
Number of pages11
JournalInorganic Chemistry
Volume49
Issue number24
DOIs
StatePublished - Dec 20 2010

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Excited states
Benzene
Derivatives
Dimers
fragments
synthesis
Metals
Ligands
Molecules
Microwave heating
Electrons
X ray crystallography
benzene
dimers
Quantum yield
analogs
excitation
Platinum
Ground state
Functional groups

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Facile synthesis and characterization of phosphorescent Pt(N ^C^N)X complexes. / Wang, Zixing; Turner, Eric; Mahoney, Vanessa; Madakuni, Sijesh; Groy, Thomas; Li, Jian.

In: Inorganic Chemistry, Vol. 49, No. 24, 20.12.2010, p. 11276-11286.

Research output: Contribution to journalArticle

Wang, Z, Turner, E, Mahoney, V, Madakuni, S, Groy, T & Li, J 2010, 'Facile synthesis and characterization of phosphorescent Pt(N ^C^N)X complexes', Inorganic Chemistry, vol. 49, no. 24, pp. 11276-11286. https://doi.org/10.1021/ic100740e
Wang, Zixing ; Turner, Eric ; Mahoney, Vanessa ; Madakuni, Sijesh ; Groy, Thomas ; Li, Jian. / Facile synthesis and characterization of phosphorescent Pt(N ^C^N)X complexes. In: Inorganic Chemistry. 2010 ; Vol. 49, No. 24. pp. 11276-11286.
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