Room-temperature and low-ordered, amphotropic-lyotropic ionic liquid crystal phases induced by alcohols in phosphonium halides.
Tri- n-decylmethylphosphonium chloride and bromide ( 1P10X) salts are not liquid crystalline. However, mesophases are induced by adding very small amounts of an alcohol or water. The temperature ranges of the induced smectic A 2 (SmA 2) liquid-crystalline phases can be very broad and the onset temperatures can be below room temperature depending upon the concentration of the alcohol or water and the structure of the alcohol. At least one molar equivalent of hydroxyl groups is necessary to convert the 1P10X completely into a liquid crystal. Strong association between the hydroxyl groups of an alcohol or water and the head groups of the 1P10X is indicated by spectroscopic, diffraction, and thermochemical data. Unlike many other smectic phases, those of the 1P10X/alcohol complexes are easily aligned in strong magnetic fields and the order parameters of selectively deuterated alcohols as measured by (2)H NMR spectroscopy, approximately 10 (-2), are much lower than the values found when the host is a commonly employed thermotropic liquid crystal. The dependence of the specific values of the order parameters on temperature, the nature of the halide anion, and the structure and concentration of the alcohol are reported. In sum, a detailed picture is presented to explain how and why an alcohol or water induces liquid crystallinity in the 1P10X salts. The data also provide a blueprint for designing media with even lower order parameters that can be hosts to determine the conformations and shapes of guest molecules.
Ma
Kefeng
K
Department of Chemistry, Georgetown University, Washington, D.C. 20057-1227, USA.
Shahkhatuni
Astghik A
AA
Somashekhar
B S
BS
Gowda
G A Nagana
GA
Tong
Yuye
Y
Khetrapal
C L
CL
Weiss
Richard G
RG
D000438:Alcohols / Q000737:chemistry; D000838:Anions; D001965:Bromides / Q000737:chemistry; D002621:Chemistry / Q000379:methods; D002627:Chemistry, Physical / Q000379:methods*; D002712:Chlorides / Q000737:chemistry; D003460:Crystallization; D050866:Liquid Crystals / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D010710:Phosphates / Q000737:chemistry*; D013696:Temperature; D013816:Thermodynamics; D014867:Water / Q000737:chemistry; D014961:X-Ray Diffraction
D000438:Alcohols; D000838:Anions; D001965:Bromides; D002712:Chlorides; D010710:Phosphates; D014867:Water