Synthetic control of Pt⋯Pt separation and photophysics of binuclear platinum complexes

Biwu Ma, Jian Li, Peter I. Djurovich, Muhammed Yousufuddin, Robert Bau, Mark E. Thompson

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Abstract

A new series of luminescent μ-pyrazolate-bridged cyclometalated platinum binuclear complexes having the formula CNPt(μ-pz-)2PtCN (CN = 2-(2,4-difluorophenyl)pyridyl, pz- = pyrazolate for 1, 3,5-dimethylpyrazolate for 2, 3-methyl-5-tert-butylpyrazolate for 3, and 3,5-bis(tert-butyl)pyrazolate for 4) have been synthesized and characterized. The two Pt(CN) moieties are bridged by two μ-pyrazolate ligands in an exo-bidentate fashion. A mononuclear complex with an isolated Pt center, CNPt(pz)2BEt2, 5, is also described. The X-ray crystal structures of 1-4 show the following Pt-Pt spacings: 1 = 3.3763(7) Å, 2 = 3.1914(9) Å, 3 = 3.0457(7) Å, and 4 = 2.8343(6) Å. At 77 K, the emission energy of the complexes varies from blue (for 1, 2, and 5) to green (for 3) to red (for 4). The changes in the photophysical properties of the binuclear complexes can be correlated with the decreasing Pt-Pt distance; the emissive state changes from a mixed ligand center triplet/metal-to-ligand charge transfer excited state (for 1 and 2) to a lower-energy, Pt-Pt metal-metal-to-ligand charge transfer state (for 3 and 4).

Original languageEnglish (US)
Pages (from-to)28-29
Number of pages2
JournalJournal of the American Chemical Society
Volume127
Issue number1
DOIs
StatePublished - Jan 12 2005
Externally publishedYes

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Platinum
Ligands
Metals
Charge transfer
Excited states
Crystal structure
X-Rays
X rays

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Synthetic control of Pt⋯Pt separation and photophysics of binuclear platinum complexes. / Ma, Biwu; Li, Jian; Djurovich, Peter I.; Yousufuddin, Muhammed; Bau, Robert; Thompson, Mark E.

In: Journal of the American Chemical Society, Vol. 127, No. 1, 12.01.2005, p. 28-29.

Research output: Contribution to journalArticle

Ma, Biwu ; Li, Jian ; Djurovich, Peter I. ; Yousufuddin, Muhammed ; Bau, Robert ; Thompson, Mark E. / Synthetic control of Pt⋯Pt separation and photophysics of binuclear platinum complexes. In: Journal of the American Chemical Society. 2005 ; Vol. 127, No. 1. pp. 28-29.
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abstract = "A new series of luminescent μ-pyrazolate-bridged cyclometalated platinum binuclear complexes having the formula CNPt(μ-pz-)2PtCN (CN = 2-(2,4-difluorophenyl)pyridyl, pz- = pyrazolate for 1, 3,5-dimethylpyrazolate for 2, 3-methyl-5-tert-butylpyrazolate for 3, and 3,5-bis(tert-butyl)pyrazolate for 4) have been synthesized and characterized. The two Pt(CN) moieties are bridged by two μ-pyrazolate ligands in an exo-bidentate fashion. A mononuclear complex with an isolated Pt center, CNPt(pz)2BEt2, 5, is also described. The X-ray crystal structures of 1-4 show the following Pt-Pt spacings: 1 = 3.3763(7) {\AA}, 2 = 3.1914(9) {\AA}, 3 = 3.0457(7) {\AA}, and 4 = 2.8343(6) {\AA}. At 77 K, the emission energy of the complexes varies from blue (for 1, 2, and 5) to green (for 3) to red (for 4). The changes in the photophysical properties of the binuclear complexes can be correlated with the decreasing Pt-Pt distance; the emissive state changes from a mixed ligand center triplet/metal-to-ligand charge transfer excited state (for 1 and 2) to a lower-energy, Pt-Pt metal-metal-to-ligand charge transfer state (for 3 and 4).",
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