Skip to main content Accessibility help
×
Home
Hostname: page-component-55597f9d44-dfw9g Total loading time: 0.192 Render date: 2022-08-10T01:35:05.871Z Has data issue: true Feature Flags: { "shouldUseShareProductTool": true, "shouldUseHypothesis": true, "isUnsiloEnabled": true, "useRatesEcommerce": false, "useNewApi": true } hasContentIssue true

Dual-Mode Optical Molecular Switching Systems for Organic Memories

Published online by Cambridge University Press:  15 March 2011

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
Get access

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.

Type
Research Article
Copyright
Copyright © Materials Research Society 2002

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1. Drexler, K.E., Nanosystems: Molecular Machinery, Manufacturing and Computation; (Wiley: New York, 1992.).Google Scholar
2. Tsivgoulis, G.M., Lehn, J.-M., Chem. Eur. J. 2, 1399 (1996).CrossRefGoogle Scholar
3. Stelacci, F., Bertarelli, C., Toscano, F., Galazzi, M.C., Zerbi, G., Chem. Phys. Let. 302, 563 (1999).CrossRefGoogle Scholar
4. Zijlstra, R.W.J., Jager, W.F., Lange, B. de, Duijnen, P.Th. van, Feringa, B.L., Goto, H., Saito, A., Koumura, N., Harada, N., J. Org. Chem. 64, 1667 (1999).CrossRefGoogle Scholar
5. Schoevaars, A.M., Kruizinga, W., Zijlstra, R.W.J., Veldman, N., Spek, A.L., Feringa, B.L., J. Org. Chem. 62, 4943 (1997).CrossRefGoogle Scholar
6. Feringa, B.L., Huck, N.P.M., Scoevaars, A.M., Adv. Mater. 8, 681 (1996).CrossRefGoogle Scholar
7. Huck, N.P.M., Jager, W.F., Lange, B. de, Feringa, B.L., Science 273, 1686 (1996); 276, 341 (1997).CrossRefGoogle Scholar
8. Jager, W.F., Jong, J.C. de, Lange, B. de, Huck, N.P.M., Meetsma, A., Feringa, B.L., Angew. Chem., Int. Ed. Engl. 34, 348 (1995).CrossRefGoogle Scholar
9. Huck, N.P.M., Feringa, B.L., J. Chem. Soc., Chem. Commun. 11, 1095 (1995).CrossRefGoogle Scholar
10. Feringa, B.L., Jager, J.F., Lange, B. de, Tetrahedron 49, 275 (1995).Google Scholar
11. Barone, P.M.V.B., Dantas, S.O., Galvão, D.S., Synth. Met. 102, 1454 (1999).CrossRefGoogle Scholar
12. Dantas, S.O., Barone, P.M.V.B., Braga, S.F., Galvão, D.S., Synth. Met. 116, 275 (2001).CrossRefGoogle Scholar
13. Dewar, M.J.S., McKee, M.L., J. Amer. Chem. Soc. 99, 5231 (1977).CrossRefGoogle Scholar
14. Dewar, M.J.S., Zoebisch, E.G., Healy, E.F., Stewart, J.J.P., J. Amer. Chem. Soc. 107, 3902. (1985).CrossRefGoogle Scholar
15. Stewart, J.J.P., J. Comp. Chem. 10, 209 (1991); 10, 221 (1991); MOPAC Program, version 6.0 Quantum Chemistry Program Exchange No. 455.CrossRefGoogle Scholar
16. Zerner, M.C., in Reviews in Computational Chemistry II, ed. Lipkowitz, K.B.; Boyd, D.B. (VCH Publishers, 1991) Chapter 8.Google Scholar
17. Scano, P., Thompson, C., J. Comp. Chem. 12, 172 (1991).CrossRefGoogle Scholar
18. Soos, Z.G., Galvão, D.S., J. Phys. Chem. 98, 1029 (1994) and references thereinCrossRefGoogle Scholar
19. Galvão, D.S., Soos, Z.G., Ramasesha, S., Etemad, S., J. Chem. Phys. 98, 3016 (1993).CrossRefGoogle Scholar
20. Barone, P.M.V.B., Dantas, S.O., Galvão, D.S., J. Mol. Struc. (THEOCHEM) 465, 219 (1999).CrossRefGoogle Scholar
21. Ridley, J., Zerner, M.C., Theor. Chim. Acta 42, 223 (1976).CrossRefGoogle Scholar
22. Edwards, W.D., Zerner, M.C., Theor. Chim. Acta 72, 347 (1987).CrossRefGoogle Scholar
23. Bolívar-Marinez, L.E., Santos, M.C. dos, Galvão, D.S., J. Phys. Chem. 100, 11029 (1996).CrossRefGoogle Scholar
24. Bolívar-Marinez, L.E., Galvão, D.S., Caldas, M.J., J. Phys. Chem B. 103, 2993 (1999).CrossRefGoogle Scholar
25.Spartan Version 4.0, Wavefunction, Inc., 1840 Von Karman Ave., #370 Irvine, CA 92715 USA, © 1995 Wavefunction, Inc.Google Scholar
26.Chem2Pac: A Computational Chemistry Integrator for Windows, Cyrillo, M. and Galvão, D.S., http://www.ifi.unicamp.br/gsonm/chem2pac.Google Scholar
27. Cyrillo, M., Galvão, D.S., Eur. Photochem. Assoc. Newsletter 67, 31 (1999).Google Scholar

Save article to Kindle

To save this article to your Kindle, first ensure coreplatform@cambridge.org is added to your Approved Personal Document E-mail List under your Personal Document Settings on the Manage Your Content and Devices page of your Amazon account. Then enter the ‘name’ part of your Kindle email address below. Find out more about saving to your Kindle.

Note you can select to save to either the @free.kindle.com or @kindle.com variations. ‘@free.kindle.com’ emails are free but can only be saved to your device when it is connected to wi-fi. ‘@kindle.com’ emails can be delivered even when you are not connected to wi-fi, but note that service fees apply.

Find out more about the Kindle Personal Document Service.

Dual-Mode Optical Molecular Switching Systems for Organic Memories
Available formats
×

Save article to Dropbox

To save this article to your Dropbox account, please select one or more formats and confirm that you agree to abide by our usage policies. If this is the first time you used this feature, you will be asked to authorise Cambridge Core to connect with your Dropbox account. Find out more about saving content to Dropbox.

Dual-Mode Optical Molecular Switching Systems for Organic Memories
Available formats
×

Save article to Google Drive

To save this article to your Google Drive account, please select one or more formats and confirm that you agree to abide by our usage policies. If this is the first time you used this feature, you will be asked to authorise Cambridge Core to connect with your Google Drive account. Find out more about saving content to Google Drive.

Dual-Mode Optical Molecular Switching Systems for Organic Memories
Available formats
×
×

Reply to: Submit a response

Please enter your response.

Your details

Please enter a valid email address.

Conflicting interests

Do you have any conflicting interests? *