An Extended chain and trinuclear complexes based on pt(II)-M (M = Tl(I), Pb(II)) bonds: Contrasting photophysical behavior

  1. Forniés, J. 1
  2. Giménez, N. 2
  3. Ibáñez, S. 1
  4. Lalinde, E. 2
  5. Martín, A. 1
  6. Moreno, M.T. 2
  1. 1 Universidad de Zaragoza

    Universidad de Zaragoza

    Zaragoza, España


  2. 2 Universidad de La Rioja

    Universidad de La Rioja

    Logroño, España


Inorganic Chemistry

ISSN: 0020-1669

Year of publication: 2015

Volume: 54

Issue: 9

Pages: 4351-4363

Type: Article

DOI: 10.1021/ACS.INORGCHEM.5B00083 SCOPUS: 2-s2.0-84929208035 WoS: WOS:000354075600024 GOOGLE SCHOLAR

More publications in: Inorganic Chemistry


Cited by

  • Scopus Cited by: 45 (12-01-2023)
  • Web of Science Cited by: 43 (06-02-2023)

JCR (Journal Impact Factor)

  • Year 2015
  • Journal Impact Factor: 4.82
  • Journal Impact Factor without self cites: 4.268
  • Article influence score: 1.001
  • Best Quartile: Q1
  • Area: CHEMISTRY, INORGANIC & NUCLEAR Quartile: Q1 Rank in area: 4/46 (Ranking edition: SCIE)

SCImago Journal Rank

  • Year 2015
  • SJR Journal Impact: 1.782
  • Best Quartile: Q1
  • Area: Inorganic Chemistry Quartile: Q1 Rank in area: 6/72
  • Area: Physical and Theoretical Chemistry Quartile: Q1 Rank in area: 21/172
  • Area: Chemistry (miscellaneous) Quartile: Q1 Rank in area: 35/460

Scopus CiteScore

  • Year 2015
  • CiteScore of the Journal : 8.5
  • Area: Inorganic Chemistry Percentile: 96
  • Area: Physical and Theoretical Chemistry Percentile: 90
  • Area: Medicine (all) Percentile: 89


The syntheses and structural characterizations of a Pt-Tl chain [{Pt(bzq)(C<inf>6</inf>F<inf>5</inf>)<inf>2</inf>}Tl(Me<inf>2</inf>CO)]<inf>n</inf> 1 and two trinuclear Pt<inf>2</inf>M clusters (NBu<inf>4</inf>)[{Pt(bzq)(C<inf>6</inf>F<inf>5</inf>)<inf>2</inf>}<inf>2</inf>Tl] 2 and [{Pt(bzq)(C<inf>6</inf>F<inf>5</inf>)<inf>2</inf>}<inf>2</inf>Pb] 3 (bzq = 7,8-benzoquinolinyl), stabilized by donor-acceptor Pt → M bonds, are reported. The one-dimensional heterometallic chain 1 is formed by alternate "Pt(bzq)(C<inf>6</inf>F<inf>5</inf>)<inf>2</inf>" and "Tl(Me<inf>2</inf>CO)" fragments, with Pt-Tl bond separations in the range of 2.961(1)-3.067(1) Å. The isoelectronic trinuclear complexes 2 (which crystallizes in three forms, namely, 2a, 2b, and 2c) and 3 present a sandwich structure in which the Tl(I) or Pb(II) is located between two "Pt(bzq)(C<inf>6</inf>F<inf>5</inf>)<inf>2</inf>" subunits. NMR studies suggest equilibria in solution implying cleavage and reformation of Pt-M bonds. The lowest-lying absorption band in the UV-vis spectra in CH<inf>2</inf>Cl<inf>2</inf> and tetrahydrofuran (THF) of 1, associated with 1MLCT/1L′LCT 1[5d<inf>π</inf>(Pt) → π∗(bzq)]/1[(C<inf>6</inf>F<inf>5</inf>) → bzq], displays a blue shift in relation to the precursor, suggesting the cleavage of the chain maintaining bimetallic Pt-Tl fragments in solution, also supported by NMR spectroscopy. In 2 and 3, it shows a blue shift in THF and a red shift in CH<inf>2</inf>Cl<inf>2</inf>, supporting a more extensive cleavage of the Pt-M bonds in THF solutions than in CH<inf>2</inf>Cl<inf>2</inf>, where the trinuclear entities are predominant. The Pt-Tl chain 1 displays in solid state a bright orange-red emission ascribed to 3MM′CT (M′ = Tl). It exhibits remarkable and fast reversible vapochromic and vapoluminescent response to donor vapors (THF and Et<inf>2</inf>O), related to the coordination/decoordination of the guest molecule to the Tl(I) ion, and mechanochromic behavior, associated with the shortening of the intermetallic Pt-Tl separations in the chain induced by grinding. In frozen solutions (THF, acetone, and CH<inf>2</inf>Cl<inf>2</inf>) 1 shows interesting luminescence thermochromism with emissions strongly dependent on the solvent, concentration, and excitation wavelengths. The Pt<inf>2</inf>Tl complex 2 shows an emission close to 1, ascribed to charge transfer from the platinum fragment to the thallium [3(L+L′)MM′CT]. 2 also shows vapoluminescent behavior in the presence of vapors of Me<inf>2</inf>CO, THF, and Et<inf>2</inf>O, although smaller and slower than those of 1. The trinuclear neutral complex Pt<inf>2</inf>Pb 3 displays a blue-shift emission band, tentatively assigned to admixture of 3MM′CT 3[Pt(d) → Pb(sp)] with some metal-mediated intraligand (3ππ/3ILCT) contribution. In contrast to 1 and 2, 3 does not show vapoluminescent behavior. © 2015 American Chemical Society.