Abstract
4-Dimethylamino-3-cyanobiphenyl (4-DMA-3-CB) was characterized with respect to linear and nonlinear optical properties in a crystal as well as in solution. The crystal structure was studied dependent on the crystallization conditions. It is shown that the crystal structure exhibiting NLO-activity can completely be solved by a combination of electron diffraction and computer modeling. There are four molecules per unit cell in the space group Pna21 with dimensions a = 10.28 Å, b = 22.64 Å, c = 5.27 Å. From this model structure the values and orientation of the dipole µ and static second order polarizability β can be calculated. Their relevance to the values obtained by a combination of polarization dependent measurements of Electric Field Induced Second Harmonic Generation (EFISH) and Hyper-Rayleigh-Scattering (HRS) in solution are discussed. The molecular second order polarizability tensor was found to be dominated by one single component. The orientations of the dipole and the vectorial parts of the second order polarizability delivered by the semiempirical calculations are in good agreement with the results of the EFISH and HRS-measurements and allow a deeper insight into the nonlinear optical properties of the crystal.
Similar content being viewed by others
References
Willets A, Rice JE, Burland DM, Shelton DP (1992) J Chem Phys 97:4590
Terhune RW, Maker PD, Savage CM (1965) Phys Rev Letters 66:681
Clays K, Persoons A (1991) Phys Rev Lett 66:2980
Clays K, Persoons A (1992) Rev Sci Instrum 63:3258
Zyss J, Van TC, Dhenaut C, Ledoux I (1993) Chem Phys 177:281
Wolff JJ, Längle D, Hillenbrand D, Wortmann R, Matschiner R, Glania C, Krämer P, Adv Mater, in press
Liptay W, Wehning D, Becker J, Rehm T, Naturforsch Z (1982) 37a: 1369
Wortmann R, Elich K, Lebus S, Liptay W, Borowicz P, Grabowska A (1992) J Phys Chem 96:9724
Heesink GJT, Ruiter AGT, van Hulst NF, Böiger B (1993) Phys Rev Lett 71:999
Andrews DL (1994) Adv Chem Phys 85:545
Verbiest T, Clays K, Samyn C, Wolff JJ, Reinhoudt D, Persoons A (1994) J Am Chem Soc 116:9320
Hendrickx E, Clays K, Persoons A, Dehu C. Brédas JL (1995) Am Chem Soc 117:3547
Andrews DL, Thirunamachandran T (1977) J Chem Phys 67:5026
Levine BF, Bethea CG (1975) J Chem Phys 63:2666
Wortmann R, Krämer P, Glania C, Lebus S, Detzer N (1993) Chem Phys 173:99,229:101 (1994)
Nye JF (1980) Physical properties of crystals
Kurtz H, Stewart J, Dieter K (1990) J Comput Chem 11:82
Clays K, Persoons A, de Maeyer L (1994) Adv Chem Phys 85:455
Cowley J (1988) Diffraction physics. North Holland
Cowley J (1992) Electron Diffraction Techniques, Vol. 1 Ed. Oxford Science Publications
Dorset D (1985) J Electron Microscopy Technique 2:89
Voigt-Martin IG, Yan DH, Gilmore C, Shankland K (1994) Ultramicroscopy 56:271
Voigt-Martin I, Schumacher M, Garbella R (1992) Macromolecules 25:961
Voigt-Martin IG, Simon P, Yan DH, Yakimaski A, Bauer S, Ringsdorf H (1995) Macromolecules 28:243
Voigt-Martin IG, Yan DH, Wortmann R, Elich K (1995) Ultramicroscopy 57: 29–43
Lequan M, Branger C, Simon J, Thami T, Chauchard E, Persoons A, Chem Phys Lett
Loos-Wildenauer M, Kunz S, Yakimanski A, Voigt-Martin IG, Wischerhoff E, Zentel R, Tschershe C, Müller M (1995) Advanced Materials, 7(2): 170–174
Crewe A, Isaacson MS, Zeitler E (1976) In: Hoppe W, Mason R, ed. Advances in Structure Research. Vol. 7 Pergamon, New York
Henderson R, Glaeser R (1985) Ultramicroscopy 16:28
Voigt-Martin I, Durst H (1987) Liquid Crystals 2:585
Voigt-Martin IG, Garbella R, Schumacher M (1994) Liquid Crystals 17: 775 801
Voigt-Martin IG, Yan DH, Yakimanski A, Schollmayer D, Gilmore CJ, Bricogne G (1995) Acta Cryst A51:849–868
Dorest D (1990) EMSA Bulletin 20:1 54–63
Dorset D (1991) Acta Cryst A 47:510
Dong W, Baird T, Fryer JR, Gilmore CJ, MacNicol DD, Bricogne G, Smith DJ, Keefe MAO, Hovmöller S (1992) Nature (Lond) 355:605
Gilmore CJ, Shankland K, Fryer JR (1993) Ultramicroscopy 49:132–146
Sheldrick GM, SHELX-86: Program for the solution of crystal structures. Univ. of Göttingen, Germany
Sheldrick GM, SHELX 93, Program for crystal structure determination, Univ. Cambridge, England
Bingham R, Dewar MS, Lo DH (1975) J Amer Chem Soc 97:1285–1295
Stewart JP (1989) Journal of Computational Chemistry 10:209–220
Mayo S, Olafson B, Goddard WA (1990) J Phys Chem 94:8897
Karasawa N, Goddard WA (1989) J Phys Chem 93:7320
Ledoux I, Zyss J, Jutant A, Amatore C (1991) Chem Phys 150:117
Zyss J, Ledoux I, Bertault M, Toupet E (1991) Chem Phys 150:125
Liptay W, In: Lim EC, Excited States, Vol. 1. Dipole moments and polarizabilities of molecules in excited electronic states, ed. (Academic Press, New York, 1974) p 129
Liptay W, Wortmann R, Schaffrin H,Burkhard O, Reitinger W, Detzer N (1988) Chem Phys 120:429
Chemla DS, Zyss J (1987) Non-linear optical properties of organic molecules and crystals. Vol. I, II ed., Academic Press
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Voigt-Martin, I.G., Zhang, Z.X., Yan, D.H. et al. Structural dependence of non-linear optical properties of 4-Dimethylamino-3-cyanobiphenyl. Colloid Polym Sci 275, 18–37 (1997). https://doi.org/10.1007/s003960050048
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/s003960050048