Metal-Stabilized Quinoidal Dibenzo[ g, p]chrysene-Fused Bis-dicarbacorrole System

Xian Sheng Ke, Yongseok Hong, Vincent M. Lynch, Dongho Kim, Jonathan L. Sessler

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

We report here a metal complexation-based strategy that permits access to a highly stable expanded porphyrin-type quinoidal polycyclic aromatic hydrocarbons (PAH). Specifically, double insertion of Pd(II) ions into a dibenzo[g,p]chrysene-fused bis-dicarbacorrole (bis-H3) gives rise to a bis-metalated species (bis-Pd) that undergoes a facile benzenoid-quinonoid transformation. In contrast to what is true for the corresponding mono-Pd(II) complex, which has organic radical character, well resolved 1H NMR and 19F NMR spectra are seen for bis-Pd. This complex is also electron paramagnetic resonance (EPR) silent over a range of temperatures. On the basis of crystallographic analyses, Raman spectroscopic studies, harmonic oscillator model of aromaticity (HOMA), and nucleus-independent chemical shift (NICS) calculations, we suggest that the dibenzo[g, p]chrysene bridge in bis-Pd has quinoidal character and that the system as a whole is a closed shell species. As expected for a quinoidal system, bis-Pd is characterized by a lowest energy absorption band that is shifted into the NIR (λmax = ca. 1420 nm (ϵ > 1.5 × 105 M-1 cm-1) for bis-Pd vs 780 nm (ϵ < 5.0 × 103 M-1 cm-1) for bis-H3). On the other hand, bis-Pd displays solvent dependent ground state and transient absorption spectral features. Such findings provide support for a zwitterionic resonance contribution to what is a predominantly a quinonoid-type ground state. The use of specific metalation to fine-tune the electronic features of polytopic ligands, as reported here, opens the door to what might be a potentially generalizable approach to the design of quinoidal PAH structures with long wavelength solvatochromic absorption features.

Original languageEnglish
Pages (from-to)7579-7586
Number of pages8
JournalJournal of the American Chemical Society
Volume140
Issue number24
DOIs
Publication statusPublished - 2018 Jun 20

Fingerprint

Polycyclic Aromatic Hydrocarbons
Polycyclic aromatic hydrocarbons
Ground state
Metals
Nuclear magnetic resonance
Porphyrins
Energy absorption
Chemical shift
Complexation
Paramagnetic resonance
Absorption spectra
Ligands
Electron Spin Resonance Spectroscopy
Ions
Wavelength
Temperature
chrysene

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Ke, Xian Sheng ; Hong, Yongseok ; Lynch, Vincent M. ; Kim, Dongho ; Sessler, Jonathan L. / Metal-Stabilized Quinoidal Dibenzo[ g, p]chrysene-Fused Bis-dicarbacorrole System. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 24. pp. 7579-7586.
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Metal-Stabilized Quinoidal Dibenzo[ g, p]chrysene-Fused Bis-dicarbacorrole System. / Ke, Xian Sheng; Hong, Yongseok; Lynch, Vincent M.; Kim, Dongho; Sessler, Jonathan L.

In: Journal of the American Chemical Society, Vol. 140, No. 24, 20.06.2018, p. 7579-7586.

Research output: Contribution to journalArticle

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T1 - Metal-Stabilized Quinoidal Dibenzo[ g, p]chrysene-Fused Bis-dicarbacorrole System

AU - Ke, Xian Sheng

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AU - Sessler, Jonathan L.

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