π‐Orbital Interactions in Möbius‐Type Molecules as Studied by Photoelectron Spectroscopy

Abstract

SummarySome benzobarrelenes were studied by photoelectron (PE.) spectroscopy. The results can be interpreted by considering dominant through-space interaction of the n-molecular fragments in a Miibius-fashion. Some chemical features of the substrates are rationalized on the basis of these findings.

Reaction Electronic Flux Perspective on the Mechanism of the Zimmerman Di-π-methane Rearrangement

“…Indeed, barrelene is an antiaromatic Möbius system like cyclobutadiene is an antiaromatic Hückel system . Note that the benzo groups in DBB do not affect the Möbius character of barrelene . On the other hand, the reaction product (i.e, SBV ) is a Hückel system (Scheme ) since the extended delocalized π-system is disrupted in T 1 upon sensibilization.…”

Synthesis of [CH2C(CO2Et)2CH2Ar]n polymers and their unique optical properties by through‐space interactions between Ar and CO groups

“…Meanwhile, through‐space and through‐bond interactions between π systems that are tethered by one or more saturated carbon atoms in organic molecules such as artificial aliphatic–aromatic systems or systems involving biomolecules such as proteins and DNA are important for understanding the electronic interactions that affect the spectroscopic properties, reactivities, and electric conductivities of the systems 6–15…”

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Polymers of type [ACH 2 C(CO 2 Et) 2 CH 2 ArA] n (Ar ¼ 1,4phenylene,2,9,or 1, were synthesized by alkylation of diethyl malonate with XCH 2 ArCH 2 X (X ¼ Cl or Br). These polymers exhibited unexpectedly enhanced UV absorption and strong, broad, bathochromically shifted fluorescence spectra compared with the parent Ar compounds.

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“…Meanwhile, through-space and through-bond interactions between p systems that are tethered by one or more saturated carbon atoms in organic molecules such as artificial aliphaticaromatic systems or systems involving biomolecules such as proteins and DNA are important for understanding the electronic interactions that affect the spectroscopic properties, reactivities, and electric conductivities of the systems. [6][7][8][9][10][11][12][13][14][15] Herein, we report the polymers of type [ACH 2 C (CO 2 Et) 2 CH 2 ArA] n , where Ar is 1,4-phenylene, 2,6-naphthylene, 9,10-anthrylene, or 1,4-phenylene-ethynylene-1,4-phenylene tethered 2,2-di(ethoxycarbonyl)trimethylene group, that exhibit an unexpectedly broad, bathochromically shifted UV absorption and fluorescent emission, the origin of which was postulated to be due to a configuration interaction between the p!p* excitation of the aromatic moiety and the n!p* excitation of carbonyl moiety on the trimethylene tether with an intramolecular charge transfer character.…”

Crystal structure of Cs+[(XeOF4)3F]- and vibrational study of the oxygen-18-enriched [XeOF5]- and [(XeOF4)3F]- anions

“…24, No. e, 6asym(XF4) in-plane, OF3 177 (1) 205 vw b,, Sasym(XF4) out-of-plane 153 (4), 116 (6), 102 (11), 89 (13), 76 (6) lattice modes…”