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Synthesis and Characterization of Ion Pairs between Alkaline Metal Ions and Anionic Anti-Aromatic and Aromatic Hydrocarbons with ?-Conjugated Central Seven- and Eight-Membered Rings.

ABSTRACT: The synthesis, isolation and full characterization of ion pairs between alkaline metal ions (Li+, Na+, K+) and mono-anions and dianions obtained from 5H-dibenzo[a,d]cycloheptenyl (C15H11 = trop) is reported. According to Nuclear Magnetic Resonance (NMR) spectroscopy, single crystal X-ray analysis and Density Functional Theory (DFT) calculations, the trop? and trop2-• anions show anti-aromatic properties which are dependent on the counter cation M+ and solvent molecules serving as co-ligands. For comparison, the disodium and dipotassium salt of the dianion of dibenzo[a,e]cyclooctatetraene (C16H12 = dbcot) were prepared, which show classical aromatic character. A d8-Rh(I) complex of trop- was prepared and the structure shows a distortion of the C15H11 ligand into a conjugated 10? -benzo pentadienide unit-to which the Rh(I) center is coordinated-and an aromatic 6? electron benzo group which is non-coordinated. Electron transfer reactions between neutral and anionic trop and dbcot species show that the anti-aromatic compounds obtained from trop are significantly stronger reductants.

SUBMITTER: Bloch J

PROVIDER: S-EPMC7594067 | biostudies-literature | 2020 Oct

REPOSITORIES: biostudies-literature

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Synthesis and Characterization of Ion Pairs between Alkaline Metal Ions and Anionic Anti-Aromatic and Aromatic Hydrocarbons with π-Conjugated Central Seven- and Eight-Membered Rings.

Bloch Jan J Kradolfer Stefan S L Gianetti Thomas T Ostendorf Detlev D Dey Subal S Mougel Victor V Grützmacher Hansjörg H

Molecules (Basel, Switzerland) 20201015 20

The synthesis, isolation and full characterization of ion pairs between alkaline metal ions (Li+, Na+, K+) and mono-anions and dianions obtained from 5H-dibenzo[a,d]cycloheptenyl (C15H11 = trop) is reported. According to Nuclear Magnetic Resonance (NMR) spectroscopy, single crystal X-ray analysis and Density Functional Theory (DFT) calculations, the trop‒ and trop2-• anions show anti-aromatic proper ...[more]

PMID: 33076581

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Project description:The adsorption of helium on charged hexabenzocoronene (Hbc, C42H18), a planar polycyclic aromatic hydrocarbon (PAH) molecule of D6h symmetry, was investigated by a combination of high-resolution mass spectrometry and classical and quantum computational methods. The ion abundance of HenHbc+ complexes versus size n features prominent local anomalies at n = 14, 38, 68, 82, and a weak one at 26, indicating that for these "magic" sizes, the helium evaporation energies are relatively large. Surprisingly, the mass spectra of anionic HenHbc- complexes feature a different set of anomalies, namely at n = 14, 26, 60, and 62, suggesting that the preferred arrangement of the adsorbate atoms depends on the charge of the substrate. The results of our quantum calculations show that the adsorbate layer grows by successive filling of concentric rings that surround the central benzene ring, which is occupied by one helium atom each on either side of the substrate. The helium atoms are fairly localized in filled rings and they approximately preserve the D6h symmetry of the substrate, but helium atoms in partially filled rings are rather delocalized. The first three rings contain six atoms each; they account for magic numbers at n = 14, 26, and 38. The size of the first ring shrinks as atoms are filled into the second ring, and the position of atoms in the second ring changes from hollow sites to bridge sites as atoms are filled into the third ring. Beyond n = 38, however, the arrangement of helium atoms in the first three rings remains essentially frozen. Presumably, another ring is filled at n = 68 for cations and n = 62 for anions. The calculated structures and energies do not account for the difference between charge states, although they agree with the measurements for the cations and show that the first solvation shell of Hbc± is complete at n = 68. Beyond that size, the adsorbate layer becomes three-dimensional, and the circular arrangement of helium changes to hexagonal.

Dataset Information

Synthesis and Characterization of Ion Pairs between Alkaline Metal Ions and Anionic Anti-Aromatic and Aromatic Hydrocarbons with ?-Conjugated Central Seven- and Eight-Membered Rings.

Publications

Synthesis and Characterization of Ion Pairs between Alkaline Metal Ions and Anionic Anti-Aromatic and Aromatic Hydrocarbons with π-Conjugated Central Seven- and Eight-Membered Rings.

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