Abstract
Bowl-shaped (bowlic) liquid crystals are reviewed and new bowlic materials containing rigid tungsten-oxo calix[4]arene based cores are discussed. Tungsten-oxo calix[4]arenes with 8 and 12 dodecyloxy sidechains have been investigated and exhibit bowlic columnar phases which are stable over approximately a 200° temperature range. The uncomplexed tetra-phenol ligands display only a transient liquid crystallinity on the first heating, and the conformational rigidity provided through tungsten-oxo complexation is necessary for well behaved mesomorphism. For the 8 sidechain analog the clearing point is at 320°C and the addition of four more sidechains results in a lower clearing point at 267°C. Polarized optical microscopy and DSC indicate that the 12 sidechain analog displays a phase with the columns packed in a hexagonal lattice which is conductive to the formation of polar phases. Both complexes exhibit a pronounced tendency to bind Lewis base guests in their cavities, and DMF forms very strong complexes which were spectroscopically characterized. The DMF guest produces large effects on the phase behavior by suppressing mesomorphism and lowering the isotropic points by 115°C and 84°C for the 8 and 12 sidechain compounds respectively. This extreme sensitivity to the DMF guest is conclusive proof that bowlic tungsten-oxo calix[4]arene liquid crystals organize in head-to-tail structures.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
Similar content being viewed by others
References
H.-J. Schneider and H. Dürr (Eds.): Frontiers in Supramolecular Organic Chemistry and Photochemistry, VCH (1991).
E. Kelderman, L. Derhaeg, G. J. T. Heesink, W. Verboom, J. R. J. Engbersen, N. R. van Hulst, A. Persoons, and D. N. Reinhoudt: Angew. Chem. Int Ed. Engl. 31, 1075 (1992).
M. D. Conner, V. Janout, I. Kudelka, P. Dedek, J. Zhu, and S. L. Regen: Langmuir 9,2389 (1993).
L. Lei: Mol. Cryst. Liq. Cryst. 146, 41 (1987).
G. W. Gray (Ed.): Thermotropic Liquid Crystals: Critical Reports on Applied Chemistry Vol. 22, Society of Chemical Industry (1987).
G. W. Gray and J. W. G. Goodby: Smectic Liquid Crystals: Textures and Structures, Leonard Hill Pub., Glasgow (1984).
S. Chandrasekhar and G. S. Ranganath: Rep. Prog. Phys. 53, 57 (1990).
These materials where reported nearly simultaneously by two groups, J. Malthete and A. Collet: Nouv. J. Chim. 9, 151 (1985).
H. Zimmerman, R. Poupko, Z. Luz, and J. Billard: Z. Naturforsch., A: Phys., Phys. Chem. Kosmophys. 40A, 149 (1985).
H. Zimmerman, R. Poupko, Z. Luz, and J. Billard: Z. Naturforsch., A: Phys., Phys. Chem. Kosmophys. 41A, 1137 (1986).
A.-M. Levelut, J. Malthete, and A. Collet: J. Physique 47, 351 (1986).
J. Malthete and A. Collet: J. Am. Chem. Soc. 109, 7544 (1987).
J. M. Buisine, H. Zimmermann, R. Poupko, Z. Luz, and J. Billard: Mol. Cryst. Liq. Cryst. 151, 391 (1987).
R. Poupko, Z. Luz, N. Spielberg, and H. Zimmermann: J. Am. Chem. Soc. 111, 6094 (1989).
W. Kranig, H. W. Spiess, and H. Zimmermann: Liq. Cryst. 7, 123 (1990).
L. Wang, Z. Sun, X. Pei, and Y. Zhu: Chem. Phys. 142, 335 (1990).
G. Cometti, E. Dalcanale, A. Du vosel, and A.-M. Levelut: Chem. Commun. 163 (1990).
S. Bonsignore, G. Commetti, E. Dalcanale, and A. Du vosel: Liq. Cryst. 8, 639 (1990).
E. Dalcanale, A. Du vosel, A.-M. Levelut, and J. Malthete: Liq. Cryst. 10, 185 (1991).
G. Cometti, E. Dalcanale, A. Du vosel, and A.-M. Levelut: Liq. Cryst. 11, 93 (1992).
S. Bonsignore, A. Du vosel, G. Guglielmetti, E. Dalcanale, and F. Ugozzoli: Liq. Cryst. 13, 471 (1993).
B. Xu and T. M. Swager: J. Am. Chem. Soc. 115, 1159 (1993).
T. Komori and S. Shinkai: Chem. Lett. 1455 (1993).
T. Komori and S. Shinkai: Chem. Lett. 901 (1992).
J. W. Goodby, R. Blinc, N. A. Clark, S. T. Lagerwall, M. A. Osipov, S. A. Pikin, T. Sakurai, Y. Koshino, and B. Zeks: Ferroelectric Liquid Crystals: Principles, Properties, and Applications, Gordon and Breach Science Publishers, Amsterdam (1991).
S. R. Marder, J. E. Sohn, and G. D. Stucky (Eds.): Materials for Nonlinear Optics: Chemical Perspectives, ACS Symposium Series 455, Washington (1991).
H. Zheng, P. J. Carroll, and T. M. Swager: Liq. Cryst. 14, 1421 (1993).
A. G. Serrette and T. M. Swager: J. Am. Chem. Soc. 115, 8879 (1993).
S. Shinkai, K. Araki, J. Shibata, D. Tsugawa, and O. Manabe: J. Chem. Soc, Perkin Trans. 3333 (1990).
F. Corazza, C. Floriani, A. Chiesi-Villa, and C. Rizzoli: Inorg. Chem. 30, 4465 (1991).
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Additional information
This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.
Rights and permissions
Copyright information
© 1994 Springer Science+Business Media Dordrecht
About this chapter
Cite this chapter
Swager, T.M., Xu, B. (1994). Liquid Crystalline Calixarenes. In: Vicens, J., Asfari, Z., Harrowfield, J.M. (eds) Calixarenes 50th Anniversary: Commemorative Issue. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-0267-4_25
Download citation
DOI: https://doi.org/10.1007/978-94-011-0267-4_25
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-010-4118-8
Online ISBN: 978-94-011-0267-4
eBook Packages: Springer Book Archive