Diketonylpyridinium Cations as a Support of New Ionic Liquid Crystals and Ion-Conductive Materials: Analysis of Counter-Ion Effects
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis and Characterization
2.2. X-ray Crystal Structure of [HOOR(12)pyH][ReO4] (5)
2.3. Thermal Behavior
2.4. Variable Temperature Powder X-ray Diffraction Studies
2.5. Conductivity and Dielectric Properties
3. Materials and Methods
3.1. Materials and Physical Measurements
3.2. Preparation of 2-[3-(4-n-alkyloxyphenyl)propane-1,3-dion-1-yl]pyridinium chloride [HOOR(n)pyH]Cl (R = C6H4OCnH2n+1, n = 12, 14, 16, 18)
3.3. Preparation of 2-[3-(4-n-alkyloxyphenyl)propane-1,3-dion-1-yl]pyridinium salts [HOOR(n)pyH][A] (A = BF4−, ReO4−, CF3SO3−, NO3−; R = C6H4OCnH2n+1, n = 12, 14, 16, 18)
3.4. Preparation of 2-[3-(4-n-alkyloxyphenyl)propane-1,3-dion-1-yl]pyridinium tetrachlorocuprate(II) [HOOR(n)pyH]2[CuCl4] (R = C6H4OCnH2n+1, n = 12, 18)
4. Conclusions
- (a)
- The presence of the tetrahedral counter-ions BF4− or ReO4− did not substantially modify neither the melting points nor the mesophase stability range. However the latter was increased when NO3− was present as the counter-ion in the salt.
- (b)
- The bulkiest counter-anion CF3SO3− causes an unfavorable increase in the melting point as well as a significant narrowing of the mesophase range.
- (c)
- The modification on the chain length has no significant influence on the mesomorphic properties in the series (I–IV). In contrast, the chain length is determinant in compounds of the family V, where increasing the alkyl chains from 12 to 18 carbon atoms results in the presence of two mesophases.
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
Abbreviations
IL | Ionic Liquid |
ILC | Ionic Liquid Crystal |
LC | Liquid Crystal |
Iso | Isotropic liquid |
Cr, Cr′, Cr″ | Solid Phases |
Sm | Smectic Mesophase |
POM | Polarized light Optical Microscopy |
DSC | Differential Scanning Calorimetry |
XRD | X-ray Diffraction |
CPE | Constant Phase Element |
RC | Resistor-Capacitor |
NMR | Nuclear Magnetic Resonance |
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Family | I | II | III | IV | V |
---|---|---|---|---|---|
n/A | BF4− | ReO4− | CF3SO3− | NO3− | CuCl42− |
12 | BF4-12 (1) | ReO4-12 (5) | CF3SO3-12 (9) | NO3-12 (13) | CuCl4-12 (17) |
14 | BF4-14 (2) | ReO4-14 (6) | CF3SO3-14 (10) | NO3-14 (14) | – |
16 | BF4-16 (3) | ReO4-16 (7) | CF3SO3-16 (11) | NO3-16 (15) | – |
18 | BF4-18 (4) | ReO4-18 (8) | CF3SO3-18 (12) | NO3-18 (16) | CuCl4-18 (18) |
Compound | Transition 1 | T2/°C | ΔH/kJmol−1 | Compound | Transition 1 | T2/°C | ΔH/kJmol−1 |
---|---|---|---|---|---|---|---|
BF4-12 (1) | Cr→Cr′ | 99 | 2.0 | CF3SO3-12 (9) | Cr→Cr′ | 81 | 14.5 |
Cr′→SmA | 132 | 25.0 | Cr′→Cr″ | 98 | 2.2 | ||
SmA→Iso | 163 3 | – | Cr″→SmA→Iso | 165 | 18.7 4 | ||
BF4-14 (2) | Cr→Cr′ | 72 | 14.1 | Iso→SmA→Cr′ | 142 | −19.3 4 | |
Cr′→Cr″ | 106 | 11.9 | Cr′→Cr | 95 | −1.8 | ||
Cr″→SmA | 136 | 26.4 | CF3SO3-14 (10) | Cr→Cr′ | 116 | 8.8 | |
SmA→Iso | 170 3 | – | Cr′→SmA→Iso | 169 | 21.6 4 | ||
BF4-16 (3) | Cr→Cr′ | 83 | 10.2 | Iso→SmA | 156 | −1.0 | |
Cr′→SmA | 137 | 35.7 | SmA→Cr′ | 142 | −19.5 | ||
SmA→Iso | 176 3 | – | Cr′→Cr | 112 | −7.0 | ||
BF4-18 (4) | Cr→Cr′ | 85 | 55.0 4 | CF3SO3-16 (11) | Cr→Cr′ | 79 | 1.5 |
Cr′→Cr″ | 117 | Cr′→Cr″ | 117 | 14.1 | |||
Cr″→SmA | 133 | Cr″→SmA | 155 | 14.1 | |||
SmA→Iso | 175 3 | – | SmA→Iso | 173 | 0.2 | ||
ReO4-12 (5) | Cr→Cr′ | 106 | 13.5 | Iso→SmA | 170 | −0.8 | |
Cr′→Cr″ | 114 | 7.9 | SmA→Cr′ | 129 | −15.7 | ||
Cr″→SmA | 138 | 17.7 | Cr′→Cr | 110 | −11.4 | ||
SmA→Iso | 173 | 1.6 | CF3SO3-18 (12) | Cr→Cr′ | 84 | 5.0 | |
ReO4-14 (6) | Cr→Cr′ | 105 | 26.2 4 | Cr′→Cr″ | 116 | 13.4 | |
Cr′→Cr″ | 116 | Cr″→SmA | 150 | 11.2 | |||
Cr″→SmA | 133 | 34.7 | SmA→Iso | 192 | 0.2 | ||
SmA→Iso | 186 | 0.5 | Iso→SmA | 166 | −0.5 | ||
ReO4-16 (7) | Cr→Cr′ | 111 | 29.6 | SmA→Cr | 111 | −27.0 | |
Cr′→SmA | 135 | 18.2 | NO3-12 (13) | Cr→SmA | 124 | 41.6 4 | |
SmA→Iso | 178 | 0.8 | SmA→Iso | 132 | |||
ReO4-18 (8) | Cr→Cr′ | 77 | 2.8 | NO3-14 (14) | Cr→SmA→Iso | 135 | 48.6 4 |
Cr′→Cr″ | 107 | 22.4 | NO3-16 (15) | Cr→SmA→Iso | 136 | 56.4 4 | |
Cr″→SmA | 127 | 5.4 | NO3-18 (16) | Cr→SmA→Iso | 135 | 50.1 4 | |
SmA→Iso | 182 | 0.2 | CuCl4-12 (17) | Cr→SmC | 110 | 32.8 | |
SmC→Iso | 185 | 54.6 | |||||
CuCl4-18 (18) | Cr→Cr′ | 79 | 73.1 4 | ||||
Cr′→SmC | 92 | ||||||
SmC→Cr″ | 108 | −34.2 | |||||
Cr″→SmC | 174 | 42.9 | |||||
SmC→Iso | 199 | 45.7 |
Compound | T/°C | 2θ/° | dobs 1/Å | dcal 1/Å | [hkl] 2 | Lattice Parameter/Å |
---|---|---|---|---|---|---|
BF4-16 (3) | 130 | 2.5 | 34.5 | 34.5 | (001) | c = 34.5 |
5.0 | 17.5 | 17.3 | (002) | |||
7.5 | 11.7 | 11.5 | (003) | |||
19 | 5.2 | – | halo | |||
ReO4-16 (7) | 140 | 1.8 | 47.0 | 47.0 | (001) | c = 47.0 |
3.6 | 24.5 | 23.5 | (002) | |||
20 | 4.9 | – | halo | |||
CF3SO3-18 (12) | 160 | 2.8 | 31.5 | 31.5 | (001) | c = 31.5 |
5.6 | 15.7 | 15.7 | (002) | |||
18 | 5.4 | – | halo | |||
NO3-12 (13) | 120 | 3.2 | 27.1 | 27.1 | (001) | c = 27.1 |
6.3 | 13.9 | 13.6 | (002) | |||
18.5 | 5.3 | – | halo | |||
CuCl4-18 (18) | 103 | 3.3 | 26.5 | 26.5 | (001) | c = 26.5 |
6.8 | 13.0 | 13.2 | (002) | |||
10.2 | 8.7 | 8.8 | (003) | |||
18.5 | 5.3 | – | halo |
[A] | EA (Solid) | EA (Mesophase) | σ410K (Ωcm)−1 |
---|---|---|---|
Cl− | 3.08/3.14 | – | 6.3 × 10−7 |
CuCl42− | 2.20 | 5.10 | 8.7 × 10−8 |
ReO4− | 2.71 | 4.61 | 8.7 × 10−6 |
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Pastor, M.J.; Cuerva, C.; Campo, J.A.; Schmidt, R.; Torres, M.R.; Cano, M. Diketonylpyridinium Cations as a Support of New Ionic Liquid Crystals and Ion-Conductive Materials: Analysis of Counter-Ion Effects. Materials 2016, 9, 360. https://doi.org/10.3390/ma9050360
Pastor MJ, Cuerva C, Campo JA, Schmidt R, Torres MR, Cano M. Diketonylpyridinium Cations as a Support of New Ionic Liquid Crystals and Ion-Conductive Materials: Analysis of Counter-Ion Effects. Materials. 2016; 9(5):360. https://doi.org/10.3390/ma9050360
Chicago/Turabian StylePastor, María Jesús, Cristián Cuerva, José A. Campo, Rainer Schmidt, María Rosario Torres, and Mercedes Cano. 2016. "Diketonylpyridinium Cations as a Support of New Ionic Liquid Crystals and Ion-Conductive Materials: Analysis of Counter-Ion Effects" Materials 9, no. 5: 360. https://doi.org/10.3390/ma9050360