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Dual-Mode Optical Molecular Switching Systems for Organic Memories

Published online by Cambridge University Press:  15 March 2011

D.S. Galvão,
S.F. Braga,
P.M.V.B. Barone and
S.O. Dantas
D.S. Galvão
Affiliation:
Instituto de Física, Universidade Estadual de Campinas - UNICAMP, Campinas, São Paulo, CEP 13083-970, CP 6165, Brazil
S.F. Braga
Affiliation:
Instituto de Física, Universidade Estadual de Campinas - UNICAMP, Campinas, São Paulo, CEP 13083-970, CP 6165, Brazil
P.M.V.B. Barone
Affiliation:
Departamento de Física, Universidade Federal de Juiz de Fora - UFJF, Juiz de Fora, Minas Gerais, CEP 36036-330, Brazil
S.O. Dantas
Affiliation:
Departamento de Física, Universidade Federal de Juiz de Fora - UFJF, Juiz de Fora, Minas Gerais, CEP 36036-330, Brazil
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Abstract

The synthesis of dual-mode optical molecular switching systems has been recently achieved. These systems were based on chiral helical-shaped alkenes in which the chirality can be reversibly modulated by light. In this work we report a theoretical study on the geometric and spectroscopic properties of these structures using the well-known semi-empirical methods PM3 (Parametric Method 3) and ZINDO/S-CI (Zerner's Intermediate Neglect of Differential Overlap -Spectroscopic - Configuration Interaction). Our results show that there are two stable conformers very close in energy for each possible molecular helicity presenting a barrier of ∼40 kcal/mol for bond rotation along the main molecular axis. Under protonation these barriers increase significantly and might explain why the protonation leads to the blocking of the switching process. We propose a scheme for the switching mechanism based on charge transfer and conformational changes during the isomer interconversion.

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References

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