On the molecular and electronic structure of spiroketones and half-molecule models

V. Galasso, J. Bogdanov, Przemyslaw Maslak, D. Jones, A. Modelli

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

The equilibrium structures of three polyketones based on the 2,2′-spirobiindan skeleton (1,1′-dione, 1,3,1′-trione, and 1,3,1′,3′-tetraone), their "half-molecule" fragments (1-indanone and 2,2-dimethylindan-1,3-dione), and the indandione dimer (2,2′-dimethyl-[2,2′]-biindenyl-1,3, l′,3′-tetraone) were investigated using the density functional theory model B3LYP/6-31G(d,p). The results matched the X-ray experimental data that are available for one of the spiroketones. The electronic structure of these ketones was investigated by means of their spectroscopic properties. The NMR 13C chemical shifts, calculated by the continuous-set-of-gauge-transformations formalism with the B3LYP/6-311+G(2d,p) method, were fairly consistent with NMR observations, in particular for the carbonyl, spiro, and quaternary carbons. The He(I) photoelectron spectra were measured and interpreted by means of ab initio outer-valence-Green's-function calculations. The theoretical results consistently reproduced the energies and splittings of the uppermost bands. These bands were associated with the phenyl π orbitals and the n(CO) lone-pair orbitals of the keto groups. Electron transmission spectroscopy, with the support of calculated π* virtual orbital energies, was employed to characterize the empty levels. Strong mixing between the phenyl and carbonyl π* fragment orbitals gave rise to stable anion states. Temporary anion states with mainly carbonyl character were observed in the 1.5-2.5 eV energy range. In the spiroketones, their energy splittings increase with the number of carbonyl groups present in the molecules and indicate the occurrence of through-space interactions between the two perpendicular indan halves.

Original languageEnglish (US)
Pages (from-to)10622-10629
Number of pages8
JournalJournal of Physical Chemistry A
Volume106
Issue number44
DOIs
StatePublished - Nov 7 2002

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Molecular structure
Electronic structure
Anions
molecular structure
Nuclear magnetic resonance
electronic structure
orbitals
Molecules
Chemical shift
Dione
Carbon Monoxide
Photoelectrons
Ketones
Green's function
Dimers
Gages
Density functional theory
molecules
Carbon
fragments

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Galasso, V. ; Bogdanov, J. ; Maslak, Przemyslaw ; Jones, D. ; Modelli, A. / On the molecular and electronic structure of spiroketones and half-molecule models. In: Journal of Physical Chemistry A. 2002 ; Vol. 106, No. 44. pp. 10622-10629.
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On the molecular and electronic structure of spiroketones and half-molecule models. / Galasso, V.; Bogdanov, J.; Maslak, Przemyslaw; Jones, D.; Modelli, A.

In: Journal of Physical Chemistry A, Vol. 106, No. 44, 07.11.2002, p. 10622-10629.

Research output: Contribution to journalArticle

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T1 - On the molecular and electronic structure of spiroketones and half-molecule models

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AU - Bogdanov, J.

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