Matches in SemOpenAlex for { <https://semopenalex.org/work/W2803314256> ?p ?o ?g. }
- W2803314256 endingPage "7586" @default.
- W2803314256 startingPage "7579" @default.
- W2803314256 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." @default.
- W2803314256 created "2018-06-01" @default.
- W2803314256 creator A5000215293 @default.
- W2803314256 creator A5033746065 @default.
- W2803314256 creator A5078891698 @default.
- W2803314256 creator A5079868859 @default.
- W2803314256 creator A5084451241 @default.
- W2803314256 date "2018-05-22" @default.
- W2803314256 modified "2023-10-17" @default.
- W2803314256 title "Metal-Stabilized Quinoidal Dibenzo[<i>g</i>, <i>p</i>]chrysene-Fused Bis-dicarbacorrole System" @default.
- W2803314256 cites W1846858789 @default.
- W2803314256 cites W1901041582 @default.
- W2803314256 cites W1974606912 @default.
- W2803314256 cites W1975812595 @default.
- W2803314256 cites W1977095542 @default.
- W2803314256 cites W1978863389 @default.
- W2803314256 cites W1985732919 @default.
- W2803314256 cites W1986652077 @default.
- W2803314256 cites W1990918910 @default.
- W2803314256 cites W1993637876 @default.
- W2803314256 cites W1996036634 @default.
- W2803314256 cites W1997151511 @default.
- W2803314256 cites W1998402824 @default.
- W2803314256 cites W1998927892 @default.
- W2803314256 cites W1999403499 @default.
- W2803314256 cites W2006218480 @default.
- W2803314256 cites W2009999279 @default.
- W2803314256 cites W2015904059 @default.
- W2803314256 cites W2019801856 @default.
- W2803314256 cites W2020100107 @default.
- W2803314256 cites W2020259659 @default.
- W2803314256 cites W2023351868 @default.
- W2803314256 cites W2023719722 @default.
- W2803314256 cites W2026947394 @default.
- W2803314256 cites W2032003798 @default.
- W2803314256 cites W2039998738 @default.
- W2803314256 cites W2040735068 @default.
- W2803314256 cites W2049007504 @default.
- W2803314256 cites W2050558814 @default.
- W2803314256 cites W2051338268 @default.
- W2803314256 cites W2055015700 @default.
- W2803314256 cites W2055299546 @default.
- W2803314256 cites W2057320230 @default.
- W2803314256 cites W2058957873 @default.
- W2803314256 cites W2061177846 @default.
- W2803314256 cites W2071588921 @default.
- W2803314256 cites W2071821456 @default.
- W2803314256 cites W2077732642 @default.
- W2803314256 cites W2085723963 @default.
- W2803314256 cites W2087427549 @default.
- W2803314256 cites W2087819569 @default.
- W2803314256 cites W2089343806 @default.
- W2803314256 cites W2090777387 @default.
- W2803314256 cites W2093363981 @default.
- W2803314256 cites W2098497922 @default.
- W2803314256 cites W2121170859 @default.
- W2803314256 cites W2123411168 @default.
- W2803314256 cites W2131433132 @default.
- W2803314256 cites W2140498148 @default.
- W2803314256 cites W2149543738 @default.
- W2803314256 cites W2153968545 @default.
- W2803314256 cites W2154409806 @default.
- W2803314256 cites W2162192528 @default.
- W2803314256 cites W2163589598 @default.
- W2803314256 cites W2264178839 @default.
- W2803314256 cites W2280605787 @default.
- W2803314256 cites W2296467982 @default.
- W2803314256 cites W2312810958 @default.
- W2803314256 cites W2313904173 @default.
- W2803314256 cites W2315374211 @default.
- W2803314256 cites W2317821468 @default.
- W2803314256 cites W2317971614 @default.
- W2803314256 cites W2322940517 @default.
- W2803314256 cites W2326060799 @default.
- W2803314256 cites W2326076228 @default.
- W2803314256 cites W2327179896 @default.
- W2803314256 cites W2327760352 @default.
- W2803314256 cites W2330021655 @default.
- W2803314256 cites W2331278849 @default.
- W2803314256 cites W2333668062 @default.
- W2803314256 cites W2336661156 @default.
- W2803314256 cites W2343025945 @default.
- W2803314256 cites W2401046393 @default.
- W2803314256 cites W2513823875 @default.
- W2803314256 cites W2587574849 @default.
- W2803314256 cites W2588478311 @default.
- W2803314256 cites W2621152423 @default.
- W2803314256 cites W2626904596 @default.
- W2803314256 cites W2743614406 @default.
- W2803314256 cites W2760586319 @default.
- W2803314256 cites W2765314147 @default.
- W2803314256 cites W2766113841 @default.
- W2803314256 cites W2774552493 @default.
- W2803314256 cites W2777783498 @default.
- W2803314256 cites W2780082803 @default.
- W2803314256 cites W2952517263 @default.
- W2803314256 cites W3005178247 @default.
- W2803314256 cites W4211163151 @default.