‘Non‐Koopmans’ States in Stilbene Cations and a Remarkable Example to the «SDT‐Equation»: Indeno [2,1‐a]indene
作者： Edwin Haselbach , Urs Klemm , Rudolf Gschwind , Thomas Bally , Laurant Chassot
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摘要: The radical cations of indeno [2, 1-a]indene (1), stilbene (2) and 3, 5, 3', 5'-tetramethylstilbene (3) were prepared by γ-irradiation the neutral precursors in an electron-scavenging matrix at 77 K. Their electronic spectra recorded compared to photoelectron (PE.) precursors. results show that either fourth or fifth excited doublet state is «Non-Koopmans» type, with specific energy (D) D (2Bg)=2.74 eV (1+), =2.59 (2+), =2.49 (3+). Remarkably, 1+ possesses two states 2.7-2.8 range: 2Au («Koopmans»-type) 2Bg («Non -Koopmans»-type). «SDT»-equation approximately connecting singlet (S) triplet (T) a alternant system its cation - provided e-promotion occurs For all three between same (paired) orbitals-is satisfyingly exemplified 1: S1 = 3.92 T1= 2.06 for 1, D4 5=2.74 1+.
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