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Structure−Property Relationships for Two-Photon Absorbing Chromophores: Bis-Donor Diphenylpolyene and Bis(styryl)benzene Derivatives

Rumi, Mariacristina and Ehrlich, Jeffrey E. and Heikal, Ahmed A. and Perry, Joseph W. and Barlow, Stephen and Hu, Zhongying and McCord-Maughon, Dianne and Parker, Timothy C. and Röckel, Harald and Thayumanavan, Sankaran and Marder, Seth R. and Beljonne, David and Brédas, Jean-Luc (2000) Structure−Property Relationships for Two-Photon Absorbing Chromophores: Bis-Donor Diphenylpolyene and Bis(styryl)benzene Derivatives. Journal of the American Chemical Society, 122 (39). pp. 9500-9510. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20170517-070820521

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Abstract

The two-photon absorption properties of a series of bis dialkylamino- or diarylamino-substituted diphenylpolyenes and bis(styryl)benzenes have been investigated. Two-photon absorption cross sections, δ, as large as 1420 × 10^(-50) cm^4 s/photon-molecule have been observed for molecules with this general bis-donor structure. The effect of the type and length of the conjugated chain and of dialkylamino or diarylamino substitution on the position and magnitude of the peak two-photon absorptivity is reported. The transition dipole moments for the transitions between the ground state and the first excited singlet state (M_(ge)) and between the first and second excited singlet states (M_(ee‘)) have been estimated using experimental data from the one- and two-photon spectra. It was found that increases in chain length result mainly in an increase in M_(ge), whereas the addition of donor end groups or going from diphenylpolyene- to phenylene-vinylene-type bridges leads primarily to an increase in Mee‘. The trends in the energy of the lowest excited singlet states and in the transition moments for the diphenylpolyene series as a function of chain length are in agreement with those calculated by quantum mechanical methods. These results furnish a link between structural features in these classes of molecules and the electronic dipole couplings and state energies that control the strength of the two-photon absorption. In bis(aminophenyl)polyenes containing up to four double bonds (m) the lowest excited singlet state is a B_u state, as opposed to the case of simple polyenes and diphenylpolyenes, for which it is an A_g state for m > 2. The relationship of the state ordering in these systems with the observed values of the radiative and nonradiative decay rates is also discussed.


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http://dx.doi.org/10.1021/ja994497sDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja994497sPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja994497sPublisherSupporting Information
Additional Information:© 2000 American Chemical Society. Received 23 December 1999. Published online 13 September 2000. Published in print 1 October 2000. Support of this research by the NSF (Chemistry Division), the Air Force Office of Scientific Research (AFOSR), the Jet Propulsion Laboratory (JPL), and the Office of Naval Research (through CAMP) is gratefully acknowledged. Part of this work was performed while J.W.P. and S.R.M. were at the JPL, California Institute of Technology, Pasadena, CA. J.W.P. acknowledges support from the AFOSR Defense University Research Instrumentation Program, which provided the MOPO laser used in this work. The work in Mons was partly supported by the Belgian Federal Government IAP Program (PAI 4/11) and the Belgian National Fund for Scientific Research (FNRS). D.B. thanks the FNRS for his Research Associate position. The authors thank Jiaying Fu for technical assistance.
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Funding AgencyGrant Number
NSFUNSPECIFIED
Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
JPLUNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Belgian Federal Government IAP ProgramPAI 4/11
Fonds de la Recherche Scientifique (FNRS)UNSPECIFIED
Record Number:CaltechAUTHORS:20170517-070820521
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20170517-070820521
Official Citation:Structure−Property Relationships for Two-Photon Absorbing Chromophores:  Bis-Donor Diphenylpolyene and Bis(styryl)benzene Derivatives Mariacristina Rumi, Jeffrey E. Ehrlich, Ahmed A. Heikal, Joseph W. Perry, Stephen Barlow, Zhongying Hu, Dianne McCord-Maughon, Timothy C. Parker, Harald Röckel, Sankaran Thayumanavan, Seth R. Marder, David Beljonne, and Jean-Luc Brédas Journal of the American Chemical Society 2000 122 (39), 9500-9510 DOI: 10.1021/ja994497s
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77518
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:18 May 2017 19:02
Last Modified:18 May 2017 19:02

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