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Metallotropic liquid crystals formed by surfactant templating of molten metal halides

Nature Materials volume 5, pages 271–275 (2006)Cite this article

Abstract

Liquid crystals consist of anisotropic molecular units, and most are organic molecules. Materials incorporating metals into anisotropic molecules, described as metallomesogens, have been prepared1. Anisotropic structures such as one-dimensional chains and two-dimensional layers are frequently observed in solid-state inorganic materials, however, little is understood about structural organization in melts of such materials. Achieving liquid-crystalline behaviour in inorganic fluids should be possible if the anisotropic structure can be retained or designed into the molten phase. We demonstrated the ability to engineer zeolite-type structures into metal halide glasses and liquids2,3. In this work we have engineered lamellar, cubic and hexagonal liquid-crystalline structure in metal-halide melts by controlling the volume fraction and nature of the inorganic block (up to 80 mol%) with respect to alkylammonium surfactants. The high metal content of these liquid-crystalline systems significantly advances the field of metallomesogens, which seeks to combine magnetic, electronic, optical, redox and catalytic properties common to inorganic materials with the fluid properties of liquid crystals.

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Figure 1: Phase diagrams for CnTACl /MCl2 (n=12 and 16, M=Zn,Cu,Cd).
Figure 2: Polarized optical microscopy of representative liquid-crystalline textures.
Figure 3: Crystal structure drawings.
Figure 4: Plots of the variation in the liquid-crystal lattice spacing as a function of the mol% of inorganic metal halide.

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Acknowledgements

This work was supported by the NSF (DMR-9501370, DMR-0072828 and DMR-0305086), and general user time on beam line X7b at BNL NSLS supported by contract DE-AC02-98CH10086 with the US DOE Office of Basic Energy Sciences division of chemical sciences. J.D.M. is a Cottrell Scholar of the Research Corporation. The assistance of X7B beamline scientist J. Hanson is gratefully acknowledged. P. Boyle, S. Parkin and C. Day contributed to single-crystal X-ray data collection. NSF-REU students J. L. Brown and J. M. Duerk, ACS Project SEED student S. Townes and J.D.M.’s daughter E. L. Martin all contributed to this work. This work is in part the subject matter of US Patents 6,540,939 and 6,790,382 B2 ‘Templated Compositions of Inorganic Liquids and Glasses’.

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  1. Department of Chemistry, North Carolina State University, Raleigh, North Carolina, 27695-8204, USA

    James D. Martin, Cristin L. Keary, Todd A. Thornton, Mark P. Novotnak, Jeremey W. Knutson & Jacob C. W. Folmer

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Correspondence to James D. Martin.

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The subject matter is related to US patents, as stated in the Acknowledgements.

Supplementary information

Supplementary information

Discussion on nomenclature (PDF 43 kb)

Supplementary information

Indexing of the diffraction of the bicontinuous cubic phases (PDF 36 kb)

Supplementary information

C8TAZnCl33 (PDF 80 kb)

Supplementary information

C12TAZnCl50 (PDF 54 kb)

Supplementary information

C12ZnCl_XRDDSC (PDF 114 kb)

Supplementary information

C16CdCl_XRDDSC (PDF 129 kb)

Supplementary information

C16CuCl_XRDDSC (PDF 147 kb)

Supplementary information

C16TACaCuCl50 (PDF 69 kb)

Supplementary information

C16TACdCl50 (PDF 70 kb)

Supplementary information

C16TACuCl25 (PDF 83 kb)

Supplementary information

C16TAZnCl33 (PDF 67 kb)

Supplementary information

C16TAZnCl50 (PDF 51 kb)

Supplementary information

C16ZnCl_XRDDSC (PDF 152 kb)

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Martin, J., Keary, C., Thornton, T. et al. Metallotropic liquid crystals formed by surfactant templating of molten metal halides. Nature Mater 5, 271–275 (2006). https://doi.org/10.1038/nmat1610

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