Z/E-photoisomerizations of olefins with 4nπ- or (4n + 2)π-electron substituents: Zigzag variations in olefin properties along the T1 state energy surfaces
Journal article, 2005

A quantum chemical study has been performed to assess changes in aromaticity along the T1 state Z/E-isomerization pathways of annulenyl-substituted olefins. It is argued that the point on the T1 energy surface with highest substituent aromaticity corresponds to the minimum. According to Baird (J. Am. Chem. Soc. 1972, 94, 4941), aromaticity and antiaromaticity are interchanged when going from S0 to T1. Thus, olefins with S0 aromatic substituents (set A olefins) will be partially antiaromatic in T1 and vice versa for olefins with S 0 antiaromatic substituents (set B olefins). Twist of the C=C bond to a structure with a perpendicular orientation of the 2p(C) Orbitals ( 3p*) in T1 should lead to regaining substituent aromaticity in set A and loss of aromaticity in set B olefins. This hypothesis is verified through quantum chemical calculations of T1 energies, geometries (bond lengths and harmonic oscillator measure of aromaticity), spin densities, and nucleus independent chemical shifts whose differences along the T1 PES display zigzag dependencies on the number of π-electrons in the annulenyl substituent of the olefin. Aromaticity changes are reflected in the profiles of the T1 potential energy surfaces (T1 PESs) for Z/E-isomerizations because olefins in set A have minima at 3p* whereas those in set B have maxima at such structures. The proper combination (fusion) of the substituents of set A and B olefins could allow for design of novel optical switch compounds that isomerize adiabatically with high isomerization quantum yields.

Author

H. Kato

Uppsala University

National Metrology Institute of Japan

M. Brink

Chalmers

Helene Möllerstedt

Chalmers, Chemical and Biological Engineering

M. C. Piqueras

Universitat de Valencia

R. Crespo

Universitat de Valencia

H. Ottosson

Uppsala University

Journal of Organic Chemistry

0022-3263 (ISSN) 1520-6904 (eISSN)

Vol. 70 23 9495-9504

Subject Categories

Chemical Engineering

DOI

10.1021/jo051558y

More information

Latest update

9/10/2018