Bimetallic Pt(II)-bipyridyl-diacetylide/Ln(III) tris-diketonate adducts based on a combination of coordinate bonding and hydrogen bonding between the metal fragments

Syntheses, structures and photophysical properties

Nawal K. Al-Rasbi, Sofia Derossi, Daniel Sykes, Stephen Faulkner, Michael D. Ward

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The luminescent Pt(II) complex [Pt(4,4′-tBu2-bipy){CC-(5-pyrimidinyl)}2] (1) was prepared by coupling of [Pt(4,4′-tBu2-bipy)Cl2] with 5-ethynyl-pyrimidine, and contains two pyrimidinyl units pendant from a Pt(II) bipyridyl diacetylide core; it shows luminescence at 520 nm which is typical of Pt(II) luminophores of this type. Reaction with [Ln(hfac)3(H2O)2] (hfac = anion of hexafluoroacetylacetone) affords as crystalline solids the compounds [1 · {Ln(hfac)3(H2O)}{Ln(hfac)3(H2O)2}] (Ln = Nd, Gd, Er, Yb), in which the {Ln(hfac)3(H2O)} unit is coordinated to one pyrimidine ring via an N atom, whereas the {Ln(hfac)3(H2O)2} unit is associated with two N atoms, one from each pyrimidine ring of 1, via N⋯HOH hydrogen-bonding interactions involving the coordinated water ligands on the lanthanide centre. Solution spectroscopic studies show that the luminescence of 1 is partly quenched on addition of [Ln(hfac)3(H2O)2] (Ln = Er, Nd) by formation of Pt(II)/Ln(III) adducts in which Pt(II)→Ln(III) photoinduced energy-transfer occurs to the low-lying f-f levels of the Ln(III) centre. Significant quenching occurs with both Er(III) and Nd(III) because both have several f-f states which match well the 3MLCT emission energy of 1. Time-resolved luminescence studies show that Pt(II)→Er(III) energy-transfer (7.0 × 107 M-1) is around three times faster than Pt(II)→Nd(III) energy-transfer (≈2 × 107 M-1) over the same distance because the luminescence spectrum of 1 overlaps better with the absorption spectrum of Er(III) than with Nd(III). In contrast Yb(III) causes no significant quenching of 1 because it has only a single f-f excited level which is a poor energy match for the Pt(II)-based excited state.

Original languageEnglish
Pages (from-to)227-232
Number of pages6
JournalPolyhedron
Volume28
Issue number2
DOIs
Publication statusPublished - Feb 3 2009

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2,2'-Dipyridyl
adducts
Luminescence
Hydrogen bonds
pyrimidines
Metals
fragments
Energy transfer
luminescence
energy transfer
hydrogen
synthesis
metals
Quenching
quenching
Lanthanoid Series Elements
Atoms
rings
Rare earth elements
Excited states

Keywords

  • Crystal structure
  • Energy-transfer
  • Lanthanides
  • Luminescence
  • Platinum

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Materials Chemistry
  • Physical and Theoretical Chemistry

Cite this

Bimetallic Pt(II)-bipyridyl-diacetylide/Ln(III) tris-diketonate adducts based on a combination of coordinate bonding and hydrogen bonding between the metal fragments : Syntheses, structures and photophysical properties. / Al-Rasbi, Nawal K.; Derossi, Sofia; Sykes, Daniel; Faulkner, Stephen; Ward, Michael D.

In: Polyhedron, Vol. 28, No. 2, 03.02.2009, p. 227-232.

Research output: Contribution to journalArticle

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abstract = "The luminescent Pt(II) complex [Pt(4,4′-tBu2-bipy){CC-(5-pyrimidinyl)}2] (1) was prepared by coupling of [Pt(4,4′-tBu2-bipy)Cl2] with 5-ethynyl-pyrimidine, and contains two pyrimidinyl units pendant from a Pt(II) bipyridyl diacetylide core; it shows luminescence at 520 nm which is typical of Pt(II) luminophores of this type. Reaction with [Ln(hfac)3(H2O)2] (hfac = anion of hexafluoroacetylacetone) affords as crystalline solids the compounds [1 · {Ln(hfac)3(H2O)}{Ln(hfac)3(H2O)2}] (Ln = Nd, Gd, Er, Yb), in which the {Ln(hfac)3(H2O)} unit is coordinated to one pyrimidine ring via an N atom, whereas the {Ln(hfac)3(H2O)2} unit is associated with two N atoms, one from each pyrimidine ring of 1, via N⋯HOH hydrogen-bonding interactions involving the coordinated water ligands on the lanthanide centre. Solution spectroscopic studies show that the luminescence of 1 is partly quenched on addition of [Ln(hfac)3(H2O)2] (Ln = Er, Nd) by formation of Pt(II)/Ln(III) adducts in which Pt(II)→Ln(III) photoinduced energy-transfer occurs to the low-lying f-f levels of the Ln(III) centre. Significant quenching occurs with both Er(III) and Nd(III) because both have several f-f states which match well the 3MLCT emission energy of 1. Time-resolved luminescence studies show that Pt(II)→Er(III) energy-transfer (7.0 × 107 M-1) is around three times faster than Pt(II)→Nd(III) energy-transfer (≈2 × 107 M-1) over the same distance because the luminescence spectrum of 1 overlaps better with the absorption spectrum of Er(III) than with Nd(III). In contrast Yb(III) causes no significant quenching of 1 because it has only a single f-f excited level which is a poor energy match for the Pt(II)-based excited state.",
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AU - Al-Rasbi, Nawal K.

AU - Derossi, Sofia

AU - Sykes, Daniel

AU - Faulkner, Stephen

AU - Ward, Michael D.

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N2 - The luminescent Pt(II) complex [Pt(4,4′-tBu2-bipy){CC-(5-pyrimidinyl)}2] (1) was prepared by coupling of [Pt(4,4′-tBu2-bipy)Cl2] with 5-ethynyl-pyrimidine, and contains two pyrimidinyl units pendant from a Pt(II) bipyridyl diacetylide core; it shows luminescence at 520 nm which is typical of Pt(II) luminophores of this type. Reaction with [Ln(hfac)3(H2O)2] (hfac = anion of hexafluoroacetylacetone) affords as crystalline solids the compounds [1 · {Ln(hfac)3(H2O)}{Ln(hfac)3(H2O)2}] (Ln = Nd, Gd, Er, Yb), in which the {Ln(hfac)3(H2O)} unit is coordinated to one pyrimidine ring via an N atom, whereas the {Ln(hfac)3(H2O)2} unit is associated with two N atoms, one from each pyrimidine ring of 1, via N⋯HOH hydrogen-bonding interactions involving the coordinated water ligands on the lanthanide centre. Solution spectroscopic studies show that the luminescence of 1 is partly quenched on addition of [Ln(hfac)3(H2O)2] (Ln = Er, Nd) by formation of Pt(II)/Ln(III) adducts in which Pt(II)→Ln(III) photoinduced energy-transfer occurs to the low-lying f-f levels of the Ln(III) centre. Significant quenching occurs with both Er(III) and Nd(III) because both have several f-f states which match well the 3MLCT emission energy of 1. Time-resolved luminescence studies show that Pt(II)→Er(III) energy-transfer (7.0 × 107 M-1) is around three times faster than Pt(II)→Nd(III) energy-transfer (≈2 × 107 M-1) over the same distance because the luminescence spectrum of 1 overlaps better with the absorption spectrum of Er(III) than with Nd(III). In contrast Yb(III) causes no significant quenching of 1 because it has only a single f-f excited level which is a poor energy match for the Pt(II)-based excited state.

AB - The luminescent Pt(II) complex [Pt(4,4′-tBu2-bipy){CC-(5-pyrimidinyl)}2] (1) was prepared by coupling of [Pt(4,4′-tBu2-bipy)Cl2] with 5-ethynyl-pyrimidine, and contains two pyrimidinyl units pendant from a Pt(II) bipyridyl diacetylide core; it shows luminescence at 520 nm which is typical of Pt(II) luminophores of this type. Reaction with [Ln(hfac)3(H2O)2] (hfac = anion of hexafluoroacetylacetone) affords as crystalline solids the compounds [1 · {Ln(hfac)3(H2O)}{Ln(hfac)3(H2O)2}] (Ln = Nd, Gd, Er, Yb), in which the {Ln(hfac)3(H2O)} unit is coordinated to one pyrimidine ring via an N atom, whereas the {Ln(hfac)3(H2O)2} unit is associated with two N atoms, one from each pyrimidine ring of 1, via N⋯HOH hydrogen-bonding interactions involving the coordinated water ligands on the lanthanide centre. Solution spectroscopic studies show that the luminescence of 1 is partly quenched on addition of [Ln(hfac)3(H2O)2] (Ln = Er, Nd) by formation of Pt(II)/Ln(III) adducts in which Pt(II)→Ln(III) photoinduced energy-transfer occurs to the low-lying f-f levels of the Ln(III) centre. Significant quenching occurs with both Er(III) and Nd(III) because both have several f-f states which match well the 3MLCT emission energy of 1. Time-resolved luminescence studies show that Pt(II)→Er(III) energy-transfer (7.0 × 107 M-1) is around three times faster than Pt(II)→Nd(III) energy-transfer (≈2 × 107 M-1) over the same distance because the luminescence spectrum of 1 overlaps better with the absorption spectrum of Er(III) than with Nd(III). In contrast Yb(III) causes no significant quenching of 1 because it has only a single f-f excited level which is a poor energy match for the Pt(II)-based excited state.

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KW - Luminescence

KW - Platinum

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