TY - JOUR
T1 - Equivalence of the Energy Gaps.ΔI(1,2) and ΔE(1,2) Between Corresponding Bands in the Photoelectron (I) and Electronic Absorption (E) Spectra of Spiro[4.4]nonatetraene. An Amusing Consequence of Spiroconjugation
AU - Batich, C.
AU - Heilbronner, E.
AU - Rommel, Erika
AU - Semmelhack, M. F.
AU - Foos, J. S.
PY - 1974/12/1
Y1 - 1974/12/1
N2 - Correlation of the photoelectron (PE) spectra of spiro[4.4]nonatetraene (1), spiro[4.4]nona-1,3,7-triene (2), spiro[4.4]nona-1,3,6-triene (3), and spiro[4.4]nona-1,3-diene (4) yields the assignment of the first three bands at 7.99, 9.22, and 10.55 eV in the PE spectrum of 1 (symmetry D2d) to ionization processes in which the photoelectron vacates the molecular orbitals 1a2(π), lb1(π), and 7e(π), respectively. The difference ΔI(1,2) = 1.23 eV between the positions of the first two PE bands of 1 is equal, within the limits of error, to the difference ΔE (1,2) ≈ 1.2 to 1.3 eV between the first two bands 8e(π*)← 1a2(π) and 8e(π*)←1b1(π) in the electronic absorption spectrum of 1. It is shown that this correspondence is the consequence of spiroconjugation between two identical alternant subsystems in a molecule of D2d symmetry, e.g., in 1.
AB - Correlation of the photoelectron (PE) spectra of spiro[4.4]nonatetraene (1), spiro[4.4]nona-1,3,7-triene (2), spiro[4.4]nona-1,3,6-triene (3), and spiro[4.4]nona-1,3-diene (4) yields the assignment of the first three bands at 7.99, 9.22, and 10.55 eV in the PE spectrum of 1 (symmetry D2d) to ionization processes in which the photoelectron vacates the molecular orbitals 1a2(π), lb1(π), and 7e(π), respectively. The difference ΔI(1,2) = 1.23 eV between the positions of the first two PE bands of 1 is equal, within the limits of error, to the difference ΔE (1,2) ≈ 1.2 to 1.3 eV between the first two bands 8e(π*)← 1a2(π) and 8e(π*)←1b1(π) in the electronic absorption spectrum of 1. It is shown that this correspondence is the consequence of spiroconjugation between two identical alternant subsystems in a molecule of D2d symmetry, e.g., in 1.
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U2 - 10.1021/ja00832a011
DO - 10.1021/ja00832a011
M3 - Article
AN - SCOPUS:0000869355
SN - 0002-7863
VL - 96
SP - 7662
EP - 7668
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 25
ER -