Triazolium based ionic liquid crystals: Effect of asymmetric substitution

Stappert, K.; Mudring, A. -V.

doi:10.1039/c4ra14961k

Triazolium based ionic liquid crystals: Effect of asymmetric substitution

Journal Article · Tue Jan 27 00:00:00 EST 2015 · RSC Advances

DOI:https://doi.org/10.1039/c4ra14961k· OSTI ID:1239144

Stappert, K. ^[1]; Mudring, A. -V. ^[2]

Ruhr-Univ. Bochum, Bochum (Germany)
Ruhr-Univ. Bochum, Bochum (Germany); Ames Lab., Ames, IA (United States)

A new series of ten different asymmetrical 1-dodecyl-3-alkyl-triazolium bromides, [C₁₂C_nTr][Br], has been synthesized and their mesomorphic behavior studied by DSC (differential scanning calorimetry), POM (polarizing optical microscopy) and SAXS (small angle X-ray scattering). The influence of the chain length of the triazolium salts is investigated to explore the effect of asymmetric substitution on the phase behaviour of these compounds. For that reason, the length of one alkyl chain was varied from 14 to 1 carbon atoms (n = 14, 12, 10, 8–4, 2, 1) while the other alkyl chain was kept at 12 carbon. Single crystal X-ray structure analysis of compounds [C₁₂C₁₂Tr][Br] and [C₁₂C₅Tr][Br] reveal that the cations adopt a U-shaped conformation with head-to-head arranged triazolium cores. In contrast, for [C₁₂C₁Tr][Br], a rod like shape of the cation with interdigitated alkyl chains is found. All investigated compounds are thermotropic liquid crystals. Higher ordered smectic phases, smectic C as well as smectic A phases were found depending on the chain length of the cation. Moreover, the clearing point temperature decreases with decreasing chain length with exception for the n-dodecyl-3-alkyltrizoliumbromides with the two shortest alkyl chains, [C₁₂C₂Tr][Br] and [C₁₂C₁Tr][Br], which present higher clearing temperatures (86 and 156 °C) and are structurally distinctly different.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE Advanced Research Projects Agency - Energy (ARPA-E)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1239144

Report Number(s):: IS-J--8632

Journal Information:: RSC Advances, Journal Name: RSC Advances Journal Issue: 22 Vol. 5; ISSN 2046-2069; ISSN RSCACL

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (57)

One-Pot Synthesis of Luminescent Polymer-Nanoparticle Composites from Task-Specific Ionic Liquids Campbell, Paul S.; Lorbeer, Chantal; Cybinska, Joanna Advanced Functional Materials, Vol. 23, Issue 23 https://doi.org/10.1002/adfm.201202472	journal	January 2013
Stabilizer-Free Metal Nanoparticles and Metal-Metal Oxide Nanocomposites with Long-Term Stability Prepared by Physical Vapor Deposition into Ionic Liquids Richter, Kai; Birkner, Alexander; Mudring, Anja-Verena Angewandte Chemie International Edition, Vol. 49, Issue 13 https://doi.org/10.1002/anie.200901562	journal	February 2010
Pyrrolidinium Ionic Liquid Crystals Goossens, Karel; Lava, Kathleen; Nockemann, Peter Chemistry - A European Journal, Vol. 15, Issue 3 https://doi.org/10.1002/chem.200801566	journal	January 2009
Highly Luminescent and Color-Tunable Salicylate Ionic Liquids Campbell, Paul S.; Yang, Mei; Pitz, Demian Chemistry - A European Journal, Vol. 20, Issue 16 https://doi.org/10.1002/chem.201301363	journal	March 2014
Reactivity of Ionic Liquids Chowdhury, Shahana; Mohan, Ram S.; Scott, Janet L. ChemInform, Vol. 38, Issue 22 https://doi.org/10.1002/chin.200722251	journal	May 2007
Surface-Functionalized Ionic Liquid Crystal-Supported Ionic Liquid Phase Materials: Ionic Liquid Crystals in Mesopores Kohler, Florian T. U.; Morain, Bruno; Weiß, Alexander ChemPhysChem, Vol. 12, Issue 18 https://doi.org/10.1002/cphc.201100379	journal	November 2011
Imidazolium based ionic liquid crystals: structure, photophysical and thermal behaviour of [C _n mim]Br·xH ₂ O (n = 12, 14; x=0, 1) Getsis, A.; Mudring, A. -V. Crystal Research and Technology, Vol. 43, Issue 11 https://doi.org/10.1002/crat.200800345	journal	November 2008
Ionic Liquid-based Synthesis-A Low-Temperature Route to Nanophosphates Cybinska, Joanna; Lorbeer, Chantal; Zych, Eugeniusz ChemSusChem, Vol. 4, Issue 5 https://doi.org/10.1002/cssc.201100095	journal	April 2011
Sonochemical Synthesis of 0D, 1D, and 2D Zinc Oxide Nanostructures in Ionic Liquids and Their Photocatalytic Activity Alammar, Tarek; Mudring, Anja-Verena ChemSusChem, Vol. 4, Issue 12 https://doi.org/10.1002/cssc.201100263	journal	December 2011
Ionic Liquid-Assisted Route to Nanocrystalline Single-Phase Phosphors for White Light-Emitting Diodes Lorbeer , Chantal; Mudring , Anja-Verena ChemSusChem, Vol. 6, Issue 12 https://doi.org/10.1002/cssc.201200915	journal	November 2013
A Luminescent Ionic Liquid Crystal: [C12mim]4[EuBr6]Br Getsis, Anna; Tang, Sifu; Mudring, Anja-Verena European Journal of Inorganic Chemistry, Vol. 2010, Issue 14 https://doi.org/10.1002/ejic.200901220	journal	March 2010
Switchable Green and White Luminescence in Terbium-Based Ionic Liquid Crystals Getsis, Anna; Mudring, Anja-Verena European Journal of Inorganic Chemistry, Vol. 2011, Issue 21 https://doi.org/10.1002/ejic.201100168	journal	June 2011
Crystalline and Liquid Crystalline Organic-Inorganic Hybrid Salts with Cation-Sensitized Hexanuclear Molybdenum Cluster Complex Anion Luminescence Bäcker, Joanna; Mihm, Svenja; Mallick, Bert European Journal of Inorganic Chemistry, Vol. 2011, Issue 26 https://doi.org/10.1002/ejic.201100365	journal	August 2011
Structural and Thermal Behaviour of the Pyrrolidinium Based Ionic Liquid Crystals [C ₁₀ mpyr]Br and [C ₁₂ mpyr]Br Getsis, Anna; Mudring, Anja-Verena Zeitschrift für anorganische und allgemeine Chemie, Vol. 635, Issue 13-14 https://doi.org/10.1002/zaac.200900216	journal	November 2009
Lanthanide Containing Ionic Liquid Crystals: EuBr2, SmBr3, TbBr3 and DyBr3 in C12mimBr Getsis, Anna; Mudring, Anja-Verena Zeitschrift für anorganische und allgemeine Chemie, Vol. 636, Issue 9-10 https://doi.org/10.1002/zaac.201000070	journal	May 2010
Reactivity of ionic liquids Chowdhury, Shahana; Mohan, Ram S.; Scott, Janet L. Tetrahedron, Vol. 63, Issue 11 https://doi.org/10.1016/j.tet.2006.11.001	journal	March 2007
DESIGNER SOLVENTS: Ionic liquids may boost clean technology development Freemantle, Michael Chemical & Engineering News, Vol. 76, Issue 13 https://doi.org/10.1021/cen-v076n013.p032	journal	March 1998
Europium(III) Fluoride Nanoparticles from Ionic Liquids: Structural, Morphological, and Luminescent Properties Lorbeer, Chantal; Cybińska, Joanna; Mudring, Anja-Verena Crystal Growth & Design, Vol. 11, Issue 4 https://doi.org/10.1021/cg101140r	journal	April 2011
Solid-State Structures of Double-Long-Chain Imidazolium Ionic Liquids: Influence of Anion Shape on Cation Geometry and Crystal Packing Wang, Xinjiao; Vogel, Carola S.; Heinemann, Frank W. Crystal Growth & Design, Vol. 11, Issue 5 https://doi.org/10.1021/cg200169u	journal	May 2011
On the Mesophase Formation of 1,3-Dialkylimidazolium Ionic Liquids Yang, Mei; Mallick, Bert; Mudring, Anja-Verena Crystal Growth & Design, Vol. 13, Issue 7 https://doi.org/10.1021/cg4004593	journal	June 2013
A Systematic Study on the Mesomorphic Behavior of Asymmetrical 1-Alkyl-3-dodecylimidazolium Bromides Yang, Mei; Mallick, Bert; Mudring, Anja-Verena Crystal Growth & Design, Vol. 14, Issue 4 https://doi.org/10.1021/cg401396n	journal	February 2014
Dysprosium-Based Ionic Liquid Crystals: Thermal, Structural, Photo- and Magnetophysical Properties Getsis, Anna; Balke, Benjamin; Felser, Claudia Crystal Growth & Design, Vol. 9, Issue 10 https://doi.org/10.1021/cg900463b	journal	October 2009
Small-Angle X-ray Scattering Studies of Liquid Crystalline 1-Alkyl-3-methylimidazolium Salts Bradley, A. E.; Hardacre, C.; Holbrey, J. D. Chemistry of Materials, Vol. 14, Issue 2 https://doi.org/10.1021/cm010542v	journal	February 2002
Structural Studies of Crystalline 1-Alkyl-3-Methylimidazolium Chloride Salts Downard, A.; Earle, M. J.; Hardacre, C. Chemistry of Materials, Vol. 16, Issue 1 https://doi.org/10.1021/cm034344a	journal	January 2004
Polyfluoroalkyl, Polyethylene Glycol, 1,4-Bismethylenebenzene, or 1,4-Bismethylene-2,3,5,6-Tetrafluorobenzene Bridged Functionalized Dicationic Ionic Liquids: Synthesis and Properties as High Temperature Lubricants Zeng, Zhuo; Phillips, Benjamin S.; Xiao, Ji-Chang Chemistry of Materials, Vol. 20, Issue 8 https://doi.org/10.1021/cm703693r	journal	April 2008
Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis Welton, Thomas Chemical Reviews, Vol. 99, Issue 8, p. 2071-2084 https://doi.org/10.1021/cr980032t	journal	August 1999
Synthesis of 1,3-Dialkyl-1,2,3-triazolium Ionic Liquids and Their Applications to the Baylis−Hillman Reaction Jeong, Yunkyung; Ryu, Jae-Sang The Journal of Organic Chemistry, Vol. 75, Issue 12 https://doi.org/10.1021/jo100618d	journal	June 2010
A Novel Modular Approach to Triazole-Functionalized Phthalocyanines Using Click Chemistry Juríček, Michal; Kouwer, Paul H. J.; Rehák, Juraj The Journal of Organic Chemistry, Vol. 74, Issue 1 https://doi.org/10.1021/jo802078f	journal	January 2009
Design Criteria for Ionic Liquid Crystalline Phases of Phosphonium Salts with Three Equivalent Long n- Alkyl Chains Ma, Kefeng; Lee, Kwang-Ming; Minkova, Liliya The Journal of Organic Chemistry, Vol. 74, Issue 5 https://doi.org/10.1021/jo802605k	journal	March 2009
Dye-Sensitized TiO ₂ Solar Cells Using Imidazolium-Type Ionic Liquid Crystal Systems as Effective Electrolytes ^† Yamanaka, Noriyo; Kawano, Ryuji; Kubo, Wataru The Journal of Physical Chemistry B, Vol. 111, Issue 18 https://doi.org/10.1021/jp0671446	journal	May 2007
White-Light-Emitting Single Phosphors via Triply Doped LaF ₃ Nanoparticles Lorbeer, Chantal; Mudring, Anja-Verena The Journal of Physical Chemistry C, Vol. 117, Issue 23 https://doi.org/10.1021/jp312411f	journal	May 2013
Piperidinium, Piperazinium and Morpholinium Ionic Liquid Crystals Lava, Kathleen; Binnemans, Koen; Cardinaels, Thomas The Journal of Physical Chemistry B, Vol. 113, Issue 28 https://doi.org/10.1021/jp903667e	journal	July 2009
A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO₂ films O'Regan, Brian; Grätzel, Michael Nature, Vol. 353, Issue 6346, p. 737-740 https://doi.org/10.1038/353737a0	journal	October 1991
Applications of ionic liquids in the chemical industry Plechkova, Natalia V.; Seddon, Kenneth R. Chem. Soc. Rev., Vol. 37, Issue 1 https://doi.org/10.1039/B006677J	journal	January 2008
Facile, environmentally friendly fabrication of porous silver monoliths using the ionic liquid N-(2-hydroxyethyl)ammonium formate Richter, Kai; Bäcker, Tobias; Mudring, Anja-Verena Chem. Commun., Issue 3 https://doi.org/10.1039/B815498H	journal	January 2009
On the dissolution of non-metallic solid elements (sulfur, selenium, tellurium and phosphorus) in ionic liquids Boros, Èva; Earle, Martyn J.; Gîlea, Manuela A. Chem. Commun., Vol. 46, Issue 5 https://doi.org/10.1039/B910469K	journal	January 2010
Facile preparation of quantum cutting GdF ₃ : Eu3+nanoparticles from ionic liquids Lorbeer, Chantal; Cybinska, Joanna; Mudring, Anja-Verena Chem. Commun., Vol. 46, Issue 4 https://doi.org/10.1039/B919732J	journal	January 2010
Ionic liquids and ionic liquid crystals of vinyl functionalized imidazolium salts Luo, Shih-Ci; Sun, Shaowen; Deorukhkar, Amol R. J. Mater. Chem., Vol. 21, Issue 6 https://doi.org/10.1039/C0JM02875D	journal	January 2011
New triazolium based ionic liquid crystals Stappert, Kathrin; Ünal, Derya; Mallick, Bert Journal of Materials Chemistry C, Vol. 2, Issue 37 https://doi.org/10.1039/C3TC31366B	journal	January 2014
Bis-cationic ionic liquid crystals Yang, Mei; Stappert, Kathrin; Mudring, Anja-Verena J. Mater. Chem. C, Vol. 2, Issue 3 https://doi.org/10.1039/C3TC31368A	journal	January 2014
First example of interdigitated U-shape benzimidazolium ionic liquid crystals Lee, Kwang Ming; Lee, Ching Kuan; Lin, Ivan J. B. Chemical Communications, Issue 9 https://doi.org/10.1039/a608517b	journal	January 1997
The phase behaviour of 1-alkyl-3-methylimidazolium tetrafluoroborates; ionic liquids and ionic liquid crystals Holbrey, John D.; Seddon, Kenneth R. Journal of the Chemical Society, Dalton Transactions, Issue 13 https://doi.org/10.1039/a902818h	journal	January 1999
A short history of ionic liquids—from molten salts to neoteric solvents Wilkes, John S. Green Chemistry, Vol. 4, Issue 2 https://doi.org/10.1039/b110838g	journal	March 2002
New ionic liquid crystals based on imidazolium salts Dobbs, William; Douce, Laurent; Allouche, Lionel New Journal of Chemistry, Vol. 30, Issue 4 https://doi.org/10.1039/b600279j	journal	January 2006
Dicationic imidazolium-based ionic liquids and ionic liquid crystals with variously positioned fluoro substituents Li, Xiaoju; Bruce, Duncan W.; Shreeve, Jean'ne M. Journal of Materials Chemistry, Vol. 19, Issue 43 https://doi.org/10.1039/b912873e	journal	January 2009
Easy access to ultra long-time stable, luminescent europium(ii) fluoride nanoparticles in ionic liquids Prondzinski, Nina von; Cybinska, Joanna; Mudring, Anja-Verena Chemical Communications, Vol. 46, Issue 24 https://doi.org/10.1039/c000817f	journal	January 2010
Stability and growth behavior of transition metal nanoparticles in ionic liquids prepared by thermal evaporation: how stable are they really? Richter, Kai; Birkner, Alexander; Mudring, Anja-Verena Physical Chemistry Chemical Physics, Vol. 13, Issue 15 https://doi.org/10.1039/c0cp02623a	journal	January 2011
Nano-biphasic ionic liquid systems composed of hydrophobic phosphonium salts and a hydrophilic ammonium salt Taguchi, Satomi; Ichikawa, Takahiro; Kato, Takashi Chemical Communications, Vol. 48, Issue 43 https://doi.org/10.1039/c2cc31074k	journal	January 2012
Phosphate protected fluoride nano-phosphors Cybińska, Joanna; Lorbeer, Chantal; Mudring, Anja-Verena Journal of Materials Chemistry, Vol. 22, Issue 19 https://doi.org/10.1039/c2jm15471d	journal	January 2012
Ultrasound-assisted synthesis of mesoporous β-Ni(OH)2 and NiO nano-sheets using ionic liquids Alammar, Tarek; Shekhah, Osama; Wohlgemuth, Jonas Journal of Materials Chemistry, Vol. 22, Issue 35 https://doi.org/10.1039/c2jm32849f	journal	January 2012
Mild yet phase-selective preparation of TiO2 nanoparticles from ionic liquids – a critical study Alammar, Tarek; Noei, Heshmat; Wang, Yuemin Nanoscale, Vol. 5, Issue 17 https://doi.org/10.1039/c3nr00824j	journal	January 2013
Small nickel nanoparticle arrays from long chain imidazolium ionic liquids Yang, Mei; Campbell, Paul S.; Santini, Catherine C. Nanoscale, Vol. 6, Issue 6 https://doi.org/10.1039/c3nr05048c	journal	January 2014
Reaching quantum yields ≫100% in nanomaterials Lorbeer, Chantal; Cybinska, Joanna; Mudring, Anja-Verena Journal of Materials Chemistry C, Vol. 2, Issue 10 https://doi.org/10.1039/c3tc31662a	journal	January 2014
Liquid-crystalline ionic liquids Bowlas, Christopher J.; Bruce, Duncan W.; Seddon, Kenneth R. Chemical Communications, Issue 14 https://doi.org/10.1039/cc9960001625	journal	January 1996
Solidification of Ionic Liquids: Theory and Techniques Mudring, Anja-Verena Australian Journal of Chemistry, Vol. 63, Issue 4 https://doi.org/10.1071/CH10017	journal	January 2010
Completion and refinement of crystal structures with SIR 92 Altomare, A.; Cascarano, G.; Giacovazzo, C. Journal of Applied Crystallography, Vol. 26, Issue 3 https://doi.org/10.1107/S0021889892010331	journal	June 1993
Thermotropic Ionic Liquid Crystals Axenov, Kirill V.; Laschat, Sabine Materials, Vol. 4, Issue 1 https://doi.org/10.3390/ma4010206	journal	January 2011

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Triazolium based ionic liquid crystals: Effect of asymmetric substitution

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