Synthesis, structural, and photophysical studies of phenylquinoline and phenylquinolinyl alkynyl based Pt(II) complexes

  1. Lalinde, E. 1
  2. Moreno, M.T. 1
  3. Ruiz, S. 1
  4. Sánchez, S. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

Journal:
Organometallics

ISSN: 0276-7333

Year of publication: 2014

Volume: 33

Issue: 12

Pages: 3078-3090

Type: Article

DOI: 10.1021/OM500336V SCOPUS: 2-s2.0-84903317580 WoS: WOS:000337936800017 GOOGLE SCHOLAR lock_openOpen access editor

More publications in: Organometallics

Metrics

Cited by

  • Scopus Cited by: 22 (11-01-2023)
  • Web of Science Cited by: 22 (06-02-2023)

JCR (Journal Impact Factor)

  • Year 2014
  • Journal Impact Factor: 4.126
  • Journal Impact Factor without self cites: 3.357
  • Article influence score: 0.871
  • Best Quartile: Q1
  • Area: CHEMISTRY, INORGANIC & NUCLEAR Quartile: Q1 Rank in area: 7/45 (Ranking edition: SCIE)
  • Area: CHEMISTRY, ORGANIC Quartile: Q1 Rank in area: 10/58 (Ranking edition: SCIE)

SCImago Journal Rank

  • Year 2014
  • SJR Journal Impact: 1.95
  • Best Quartile: Q1
  • Area: Inorganic Chemistry Quartile: Q1 Rank in area: 5/74
  • Area: Organic Chemistry Quartile: Q1 Rank in area: 14/191
  • Area: Physical and Theoretical Chemistry Quartile: Q1 Rank in area: 18/176

Scopus CiteScore

  • Year 2014
  • CiteScore of the Journal : 7.3
  • Area: Inorganic Chemistry Percentile: 94
  • Area: Organic Chemistry Percentile: 91
  • Area: Physical and Theoretical Chemistry Percentile: 87

Abstract

We present the synthesis, characterization, and photophysical properties of two series of alkynyl-platinum(II) complexes containing the phenylquinoline (Hpq) or the cyclometalated phenylquinolinyl (pq) ligand. Unusual monoanionic complexes (NBu4)[Pt(C≡CR)3(Hpq)] (R = Tol 1, C 6H4OMe-3 2, C6H4CF3-4 3) were generated in moderate yield by treatment of [Pt(pq)(μ-Cl)]2 with an excess of LiC≡CR (1:8), followed by subsequent treatment with NBu4 in iPrOH. However, a similar reaction with LiC≡C tBu evolves with formation of [Pt(pq)(μ-κC α:η2-C≡CtBu)]2 4. Related dimers [Pt(pq)(μ-κCα:η2- C≡CR)]2 (R = Tol 5, C6H4OMe-3 6, C 6H4CF3-4 7) were successfully prepared by modification of the reaction conditions. Single-crystal studies were performed on 2, 4, and 5, revealing the presence of intramolecular (H⋯Pt and H⋯C≡C) and intermolecular Omethoxy⋯H Hpq contacts in 2 and the formation of butterfly structures in 4 and 5. In the tBu derivative 4, a shorter intramolecular Pt⋯Pt separation was found [3.0936(3) Å in 4 vs 3.2109(3) Å in 5], which is related to the nature of η2-alkynyl linkages (η2-asymmetrical in 4 vs η2-symmetrical in 5). Anionic 1-3 display bright emissions in rigid media (solid, glass) with resolved side vibronic bands at 77 K. The energy of the emissions (supported by computational studies on 2) allows us to ascribe these emissions primarily to a mixed alkynyl-metal to the phenylquinoline 3[(L′ + M)LCT] excited state, being perturbed in 2 (solid) by the intermolecular O methoxy⋯HHpq contacts. Whereas diplatinum complexes 5-7 have no visible emission at 298 K in the solid state, 4 shows a structureless band (578 nm), which is significantly red-shifted at 77 K (595 nm). Theoretical studies suggest a notable distortion in the excited state in relation to S0 and identify the emission within the dimetallacycle Pt2(C≡C)2 with alkynyl to pq charge-transfer 3[(MM + L′)LCT] [with minor 3IL (pq) contribution], whereas, in 5, the emission is tentatively ascribed to a mixture of 3L′LCT with minor 3MMLCT character. The emission profiles observed in glassy solution for all 4-7 complexes (556-562 nm, CH 2Cl2) and in the solid state for 6-7 are consistent with those exhibited by mononuclear related chromophores 3[(L′ + M)LCT] (L′ = C≡CR, L = pq), suggesting negligible contribution of the Pt⋯Pt interaction. © 2014 American Chemical Society.