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Article

Evidence of Counterion Size Effect on the Stability of Columnar Phase of Ionic Liquid Crystals Based on Pyridinium Salts Derived from N-3,4,5-Tri(alkyloxy)-benzyl-4-pyridones

1
Department of Inorganic Chemistry, University of Bucharest, 4-12 Regina Elisabeta Blvd., 030018 Bucharest, Romania
2
National Institute of Materials Physics, P.O. Box MG-7, 077125 Magurele, Romania
3
Department of Physics, University Politehnica of Bucharest, Spl. Independentei 313, 060042 Bucharest, Romania
4
Department of Physical Chemistry, University of Bucharest, 4-12 Regina Elisabeta Blvd., 030018 Bucharest, Romania
*
Author to whom correspondence should be addressed.
Crystals 2022, 12(5), 715; https://doi.org/10.3390/cryst12050715
Received: 8 April 2022 / Revised: 12 May 2022 / Accepted: 13 May 2022 / Published: 17 May 2022
(This article belongs to the Special Issue Liquid Crystal Composites)

Abstract

:
The synthesis and characterization of novel ionic liquid crystals based on pyridinium salts with Br and PF6 counterions are described in this work. These pyridinium salts were derived from 4-hydroxypyridine, both by N- and O-alkylation. The 3,4,5-tri(alkyloxy)-benzyl mesogenic unit was attached to the nitrogen atom of the pyridinium ring. Alkyl chains with a different number of carbon atoms (6, 8, 10, 12 and 14) were employed in order to show the effect on the stability of mesophase. The POM (polarizing optical microscopy) and XRD (powder X-ray diffraction) studies indicated that bromide salts with shorter chains C6, C8 and C10 do not show mesomorphic properties, while longer chain analogues with C12 and C14 exhibit two enantiotropic columnar phases. Surprisingly, the pyridinium salts with the larger size PF6 counterion do not exhibit liquid crystal properties.

1. Introduction

Ionic liquid crystals (ILCs) are a distinct class of liquid crystals that have been known about for a long time. They generally consist of a positively charged cationic core and at least one long alkyl chain. These versatile materials combine the liquid crystals with ionic liquids properties. More importantly, they combine anisotropy of physical properties with ionic conductivity and low volatility [1,2]. Thus, for ILC materials, the formation of liquid crystalline (LC) phases is determined by the microphase segregation of polar (cationic core) and nonpolar (alkyl groups) domains. Several factors are known to lead to the partially ordered environments of the LC phase. These are the hydrogen bonding between cations and anions [3,4,5] and the van der Waals, electrostatic, hydrophobic and dipole-dipole interactions [6,7]. To obtain the ionic liquid crystals, the design of a conventional liquid crystal could be developed by the introduction of the desired ionic groups together with traditional mesogenic groups (mostly long alkyl chains, cyanobiphenyl units, etc.). The imidazolium, pyridinium and phosphonium cores are the most attractive candidates for this task, particularly due to their relatively easy synthetic pathways [8,9]. On the other hand, although most of the studies reported in the literature were focused on the halide salts (with bromide, chloride, or iodide anions), other counterions were also used to prepare ILCs. In many examples, these counterions have a larger size and their appropriate choice is intended to control the liquid crystalline properties or to tailor the specific applications, including the decrease in the melting points and the viscosity of the products. In this respect, many reports are dedicated to the prediction of the properties of new ILCs made through joining together known constituents, and these studies offer important knowledge on the rational design of these materials. The size of counterions was found to play a vital role in the stabilization and the type of the mesophases exhibited by ILCs [10,11,12]. Besides the halide anions, commonly used anions to obtain single charged ILCs are perfluorinated anionic species such as BF4, PF6 and CF3SO3.
The pyridinium-based ILCs are intensively investigated as these products exhibit very similar properties to the related popular imidazolium-based ILCs [13,14,15,16,17,18,19,20,21,22]. The use of pyridinium core generates a variety of molecular shapes, from calamitic to discotic materials and various liquid crystalline phases ranging from the less common nematic phase to the most commonly observed SmA phase for ionic mesogens or hexagonal columnar phases. The mesomorphic behavior of the pyridinium-based ILCs is dictated by the position and the nature of the mesogenic groups attached to the pyridinium ring, as well as the counterion employed [23,24]. Several recent reviews focused on this topic [25,26].
In this paper, we report the synthesis and the characterization of a new series of pyridinium salts obtained from 4-hydroxypyridine as a starting material and containing on one side a 3,4,5-tri(alkyloxy)benzyl mesogenic unit and on the other side an alkyloxy group, using different counterions. The 4-hydroxypiridine precursor is well known for its ability to give both O- and N-alkylated pyridinium salts [27]. In the first step 4-hydroxypyridine has been mono N-alkylated to obtain the neutral N-(3,4,5-trialkyloxybenzyl)-4-pyridones compounds, followed by a further O-alkylation of these compounds with different alkyl halides to yield the N-(3,4,5-trialkyloxybenzyl)-4-alkoxypyridinium bromide salts as new ILCs. Further, the exchange of the bromide anion with PF6 counterion provided the new family of related pyridinium salts. Our preliminary results on the C12 analogues revealed that replacing bromide ion (Br) with other counterions (NO3, BF4 and PF6) resulted in mesophase suppression [28]. The destabilization effect of the liquid crystal phase due to the use of larger counterions, such as tetrafluoroborate and hexafluorophosphate, could be, in principle, compensated by employing longer alkyl chains. For this purpose, in this study, longer C14 analogues have been prepared and investigated along with shorter analogues (C6, C8 and C10) in combination with PF6 fluorinated counterion. The molecular structures, liquid crystalline properties, thermal stability, and optical properties have been investigated by various experimental techniques, providing pertinent and exhaustive insights into the structural factors that were correlated with the stability of the liquid crystalline phases of the new pyridinium-based ILCs.

2. Materials and Methods

2.1. Materials and Measurements

All the chemicals, reagents and common solvents were supplied from Sigma-Aldrich and Merck and used as received without further purification. The synthesis and characterization of the 4-pyridone intermediates were described by us in previous reports [28,29].
1H-NMR (300 MHz) and 13C-RMN (75 MHz) spectra were obtained with a Bruker Fourier 300 or Bruker Avance III spectrometer (Bruker BioSpin NMR, Rheinstetten, Germany) using CDCl3 as a solvent. C, H, N analyses were carried out with an EuroEA 3300 (Eurovector, Pavia, Italy) instrument after drying of the samples in a vacuum. IR spectra of the samples in solid state were measured by the ATR method performed on a Bruker Tensor V-37 spectrophotometer (Bruker Optics Inc., Billerica, MA, USA) in the range of 4000–400 cm−1. The liquid crystal properties were characterized by differential scanning calorimetry using a Diamond DSC Perkin Elmer instrument (Perkin Elmer, Boston, MA, USA) operating at a scanning rate of 10 °C/min. Samples were encapsulated in aluminum pans and kept in a dry nitrogen atmosphere. Polarizing optical microscopy (POM) observations of transitions and optical textures on untreated glass slides were carried out with a Nikon 50iPol polarized optical microscope (Nikon Instruments, Melville, NY, USA) equipped with a Linkam THMS600 hot stage and TMS94 control processor (Linkam Scientific Instruments Ltd., Tadworth, UK). XRD measurements of the samples were characterized on cooling from the isotropic state by a D8 Advance diffractometer (Bruker AXS GmbH, Karlsruhe, Germany) in parallel beam setting with monochromatized Cu–Kα1 radiation (λ = 1.5406 Å), a scintillation detector, and a horizontal sample stage. A home-made heating stage adapted to the sample stage of the diffractometer was used for temperature control of the sample during the measurements. The samples were heated and cooled with a rate of 10.0 °C/min to the corresponding temperature.

2.2. Synthesis of Bromide Pyridinium Salts, 2ae

The quaternary bromide pyridinium salts were obtained by the alkylation reaction between 4-pyridone derivatives, 1ae, (1 g, 2.06 mmol) in acetonitrile and the corresponding bromoalkane (excess of CnH2n+1Br, n = 6, 8, 10, 12, 14; 6.8 mmol) under reflux in nitrogen atmosphere for 48 h (Scheme 1). After this period, the solvent was evaporated to dryness. The obtained product was purified on silica gel column chromatography using as eluent a mixture of DCM/MeOH (95:5), followed by its recrystallization from DCM and ethyl ether, resulting in white solids.
2a: 1H-NMR (CDCl3, 300 MHz): 9.24 (d, J = 7.3 Hz, 2H); 7.24 (m, 2H); 6.86 (s, 2H); 5.89 (s, 2H), 4.19 (t, J = 6.4 Hz, 2H); 3.92 (m, 6H); 2.00–1.57 (m, 8H); 1.48–1.27 (m, 24H); 0.87 (m, 12H). 13C-NMR (CDCl3, 75 MHz): 170.20, 153.76, 146.02, 138.89, 128.05, 113.44, 107.84, 73.37, 71.49, 69.42, 62.50, 31.61, 31.24, 30.20, 29.28, 28.30, 25.70, 25.25, 24.18, 22.52, 19.73, 13.88. IR (ATR, cm−1): 2928, 2858, 1642, 1591, 1520, 1467, 1443, 1329, 1255, 1110, 849, 728. Yield: 72%. Anal. Calcd for C36H60BrNO4x0.5H2O: C% 65.53, H% 9.32, N% 2.12. Anal. Found: C% 65.14, H% 9.69, N% 2.05.
2b: 1H-NMR (CDCl3, 300 MHz): 9.21 (d, J = 7.2 Hz, 2H); 7.24 (m, 2H); 6.85 (s, 2H); 5.89 (s, 2H); 4.32–4.14 (m, 2H); 3.95 (m, 6H); 1.90–1.66 (m, 8H); 1.28 (m, 40H); 0.88 (t, J = 6.5 Hz, 12H). 13C-NMR (CDCl3, 75 MHz): 170.21, 153.78, 145.99, 138.91, 128.02, 113.43, 107.85, 73.41, 71.50, 69.44, 62.53, 31.77, 30.28, 29.62, 28.91, 28.36, 26.07, 25.60, 22.59, 14.03. IR (ATR, cm−1): 2926, 2855, 1641, 1590, 1521, 1465, 1443, 1329, 1255, 1112, 850, 724. Yield: 75%. Anal. Calcd for C44H76BrNO4x0.5H2O: C% 68.46, H% 10.05, N% 1.81. Anal. Found: C% 68.09, H% 10.38, N% 1.72.
2c: 1H-NMR (CDCl3, 300 MHz): 9.17 (d, J = 7.2 Hz, 2H); 7.24 (m, 2H); 6.79 (s, 2H); 5.85 (s, 2H), 4.21 (t, J = 6.5 Hz, 2H); 3.94 (m, 6H); 1,77 (m, 8H); 1.26 (m, 56H); 0.87 (t, J = 6.7 Hz, 12H). 13C-NMR (CDCl3, 75 MHz): 171.23, 153.79, 145.87, 113.48, 107.92, 73.39, 71.52, 69.49, 62.58, 31.85, 29.84, 28.90, 28.35, 26.10, 22.65, 14.08. IR (ATR, cm−1): 2920, 2851, 1639, 1592, 1516, 1468, 1446, 1314, 1254, 1129, 849, 721. Yield: 73%. Anal. Calcd for C52H92BrNO4x0.5H2O: C% 70.63, H% 10.60, N% 1.58. Anal. Found: C% 70.27, H% 10.85, N% 1.49.
2d: 1H-NMR (CDCl3, 300 MHz): 9.18 (d, J = 7.2 Hz, 2H); 7.24 (m, 2H); 6.81(s, 2H); 5.85 (s, 2H); 4.19 (t, 2H); 3.93 (m, 6H); 1.87–1.67 (m, 8H); 1.45–1.20 (m, 72H); 0.86 (m, 12H). 13C-NMR (CDCl3, 75 MHz): 170.24, 153.81, 145.97, 138.96, 127.98, 113.46, 107.88, 73.38, 71.51, 69.48, 62.60, 31.91, 30.31, 29.70, 29.62, 29.48, 29.41, 25.64, 22.67, 14.09. IR (ATR, cm−1): 2956, 2918, 2850, 1640, 1593, 1517, 1469, 1446, 1314, 1255, 1129, 846, 720. Yield: 77%. Analytical data reported in [28].
2e: 1H-NMR (CDCl3, 300 MHz): 9.18 (d, J = 7.1 Hz, 2H); 7.24 (m, 2H); 6.81 (s, 2H); 5.85 (s, 2H), 4.28–4.04 (m, 2H); 4.04–3.81 (m, 6H); 1.96–1.57 (m, 8H); 1.24 (m, 88H); 0.85 (t, J = 6.9 Hz, 12H). 13C-NMR (75 MHz, CDCl3) δ 170.22, 153.81, 146.00, 138.96, 127.98, 113.43, 107.88, 73.38, 71.43, 69.46, 62.61, 31.90, 30.32, 29.87, 28.91, 28.39, 26.11, 25.63, 22.66, 14.09. IR (ATR, cm−1): 2917, 2849, 1640, 1592, 1519, 1469, 1444, 1307, 1255, 1121, 845, 720. Yield: 81%. Anal. Calcd for C68H124BrNO4xH2O: C% 73.08, H% 11.36, N% 1.25. Anal. Found: C% 72.78, H% 11.85, N% 1.07.

2.3. Synthesis of PF6 Pyridinium Salts, 3ae

Pyridinium salts 3ae were obtained by the metathesis reaction between bromide salts 2ae (0.155 mmol), dissolved in methanol (5 mL) and an equivalent amount of NH4PF6 (0.026 g, 0.155 mmol) dissolved in 3 mL water. The reaction mixture was stirred at room temperature for 1 h. The resulting precipitate was filtered, washed with methanol and recrystallized from CH2Cl2/Et2O.
3a: 1H-NMR (CDCl3, 300 MHz): 8.48 (d, J = 6.9 Hz, 2H); 7.25 (m, 2H); 6.65 (s, 2H); 5.42 (s, 2H); 4.20 (t, J = 6.4Hz, 2H); 3.97 (m, 6H), 1.87–1.67 (m, 8H); 1.45–1.20 (m, 24H); 0.88 (m, 12H). 13C-RMN (CDCl3, 75 MHz): 170.58, 154.01, 145.07, 139.16, 127.09, 113.72, 107.48, 73.42, 71.46, 69.32, 63.57, 31.80, 31.68, 30.32, 29.71, 29.30, 28.35, 26.10, 25.60, 22.63, 14.07. IR (ATR, cm−1): 2956, 2932, 2860, 1644, 1592, 1524, 1468, 1444, 1325, 1252, 1111, 859, 728, 557. Yield: 69%. Anal. Calcd for C36H60F6NO4P: C% 62.46, H% 8.88, N% 2.02. Anal. Found: C% 62.72, H% 9.10, N% 1.97.
3b: 1H-NMR (CDCl3, 300 MHz): 8.49 (d, J = 7.1 Hz, 2H); 7.22 (d, J = 7.1 Hz, 2H); 6.61 (s, 2H); 5.38 (s, 2H), 4.20 (t, J = 6.5 Hz, 2H); 3.93 (m, 6H), 1.77 (m, 8H); 1.33 (m, 40H); 0.87 (m, 12H).13C-NMR (CDCl3, 75 MHz): 170.59, 154.02, 145.09, 139.15, 127.09, 113.70, 107.50, 73.42, 71.49, 69.29, 63.57, 31.80, 31.70, 30.32, 29.53, 29.39, 29.20, 29.10, 28.93, 28.37, 26.07, 25.60, 22.66, 14.06. IR (ATR, cm−1): 2958, 2925, 2854, 1648, 1592, 1523, 1467, 1441, 1334, 1247, 1112, 862, 839, 723, 557. Yield: 67%. Anal. Calcd for C44H76F6NO4P: C% 63.82, H% 9.25, N% 1.69. Anal. Found: C% 63.47, H% 9.56, N% 1.63.
3c: 1H-NMR (CDCl3, 300 MHz): 8.52 (d, J = 6.7 Hz, 2H); 7.23 (m, 2H); 6.63 (s, 2H); 5.48 (s, 2H); 4.21 (t, J = 6.4 Hz, 2H); 3.94 (m, 6H), 1.73 (m, 8H); 1.26 (m, 56H); 0.87 (m, 12H). 13C-NMR (CDCl3, 75 MHz): 170.56, 154.03, 145.22, 139.24, 126.99, 113.70, 107.65, 73.44, 71.54, 69.38, 63.54, 31.91, 31.84, 30.31, 29.73, 29.64, 29.36, 29.15, 28.37, 26.08, 25.60, 22.68, 14.10. IR (ATR, cm−1): 2958, 2922, 2851, 1648, 1591, 1524, 1468, 1442, 1334, 1250, 1111, 864, 833, 721, 557. Yield: 72%. Anal. Calcd for C52H92F6NO4P: C% 66.42, H% 9.86, N% 1.49. Anal. Found: C% 66.08, H% 10.15, N% 1.28.
3d: 1H-NMR (CDCl3, 300 MHz): 8.47 (d, J = 7.3 Hz, 2H); 7.22 (d, J = 7.3 Hz, 2H); 6.60 (s, 2H); 5.37 (s, 2H), 4.20 (t, J = 6.4 Hz, 2H); 3.93 (q, J = 6.6 Hz, 6H); 1.84–1.68 (m, 8H); 1.26 (m, 72H); 0.87 (t, J = 6.6 Hz, 12H). 13C-NMR (CDCl3, 75 MHz): 170.61, 154.05; 145.07, 139.23, 127.00, 113.71, 107.55, 73.45, 71.52, 69.34, 31.93, 30.34, 29.75; 29.62, 29.54, 29.38, 29.18, 28.39, 26.10, 25.62; 22.69; 14.10. IR (ATR, cm−1): 2957, 2920, 2851, 1647, 1592, 1522, 1468, 1442, 1334, 1252, 1115, 846, 830, 721, 558. Yield: 67%. Analytical data reported in [28].
3e: 1H-NMR (CDCl3, 300 MHz): 8.51 (d, J = 6.8 Hz, 2H); 7.22 (d, J = 6.8 Hz, 2H); 6.61 (s, 2H); 5.40 (s, 2H), 4.22 (t, J = 6.4 Hz, 2H); 3.96–3.89 (m, 6H); 1.78 (m, 8H), 1.45–1.25 (m, 88H); 0.88 (t, J = 6.2 Hz, 12H). 13C-NMR (CDCl3, 75 MHz): 170.58, 154.03, 145.12, 139.18, 127.07, 113.69, 107.54, 73.43, 71.51, 69.33, 63.54, 31.93, 30.34, 29.74, 29.55, 29.45, 29.19, 28.39, 26.11, 25.62, 22.68, 14.10. IR (ATR, cm−1): 2956, 2920, 2850, 1648, 1593, 1522, 1468, 1443, 1335, 1252, 1117, 831, 721, 558. Yield: 74%. Anal. Calcd for C68H124F6NO4P: C% 70.12, H% 10.73, N% 1.20. Anal. Found: C% 70.37, H% 10.99, N% 1.06.

3. Results and Discussion

3.1. Synthesis and Characterization

The synthetic procedure employed for the preparation of the pyridinium salts with side alkyl chains of the same length is depicted in Scheme 1. The starting 4-pyridone compounds 1af were prepared by the N-alkylation of 4-hydroxypyridine based on the protocol reported elsewhere by us [28,29,30,31]. Subsequent O-alkylation with alkyl bromides in refluxing acetonitrile and in the presence of K2CO3 gave the bromide pyridinium salts 2ae in good yields of 67–81%. Salt metathesis of bromide salts 2ae in methanol with ammonium hexafluorophosphate produced the related pyridinium salts 3ae. The pyridinium salts 2ae and 3ae were characterized by 1H-NMR and 13C-RMN spectroscopy and IR spectroscopy. NMR spectroscopy is a useful tool to monitor the metathesis of the bromide ion with other various anions. For example, the 1H-NMR spectra recorded in deuterated chloroform for pyridinium salts showed that the counterion nature has a pronounced impact on the chemical shift of the two protons located in the vicinity of the pyridinium nitrogen atom. While for bromide salts 2ae, the signal corresponding to these two protons in question was located around 9.17–9.24 ppm, upfield shifts in the 8.47–8.62 ppm range were observed for the ILCs with PF6 anion 3ae. The chemical shifts followed the order Br > PF6, similar to other studies performed for different series of simple pyridinium or imidazolium when the formation of hydrogen bonds with the respective counterion can explain these observations (Figure 1) [23]. The metathesis reaction of the bromide anion with PF6 counterion was also confirmed by IR spectroscopy. Analysis of the IR spectra recorded for the pyridinium salts revealed that characteristic strong frequencies for the new PF6 group were found in the 830–840 and 550–560 cm−1 ranges (Figure 2).

3.2. Mesomorphic Properties of Pyridinium Salts

The liquid crystal properties were investigated by differential scanning calorimetry (DSC), the mesophases presented by the pyridinium salts being identified based on the characteristic textures observed by polarizing optical microscopy (POM), and the correct attribution being subsequently confirmed by powder X-ray diffraction at different temperatures (XRD). The results of the DSC measurements (transition temperatures and the related enthalpies) for all pyridinium salts are presented in Table 1. The pyridinium salts with bromide anion and alkyl chains longer than C10 exhibit an enantiotropic columnar phase assigned based on the characteristic texture observed by POM on cooling from the isotropic phase. In the first DSC heating run of C6 bromide salt (2a), only an endothermic melting transition at 31 °C was observed. This compound melts straight to the isotropic phase and no other transitions were observed during the subsequent cooling or heating runs. The same behavior was evidenced for C8 salt (2b). In the cooling run the glass transition was observed at −12 °C. The C10 salt (2c) melted to the isotropic phase at 60 °C. In addition, the second heating-cooling cycle of the C10 bromide analogue showed on heating a cold crystallization transition at 22 °C and the melting transition to the isotropic state at 60 °C (Figure 3a).
The second heating-cooling cycle of the pyridinium salts from the isotropic state revealed a good reproducibility of the mesophase. The mesomorphic behavior of the pyridinium salt 2d was fully characterized by us in a previous study [28]. Similar to compound 2d, the C14 pyridinium salt (2e) showed two separate LC phases. The transition between the two mesophases was sharp and easily observed by POM (Figure 4) and DSC (Figure 3b). The low temperature mesophase was stable down to 23 °C for 2d and to 31 °C for 2e. It was observed that the clearing temperature of the bromide salts depended strongly on the number of carbon atoms of the terminal aliphatic chains. The lowest isotropization temperature was recorded for the shortest analogue 2a with six carbon atoms in the alkyl chains and it increased with increasing the elongation of the alkyl chain. The same trend was observed for pyridinium salts with PF6 counterion 3ae. Moreover, the transition temperatures to the isotropic phase were found to be significantly lower in comparison to related bromide compounds 2ae.
Deceptively, the pyridinium salts with the PF6 counterion, 3ae, did not exhibit liquid crystal properties. For these compounds, the formation of liquid crystal phases was strongly influenced by the separation between the pyridinium ionic fragments and the hydrophobic aliphatic chains and, obviously, the counterion had a major influence on the stabilization of the mesophase. For example, a similar significant effect of the counterions was found in the related methylimidazolium salts with the 3,4,5-tris(alkyloxy)benzyl mesogenic groups [32].
The tentative assignment of the mesophases was confirmed from data analysis obtained by X-ray powder diffraction, recorded at different temperatures (Figure 5 and Table 2). The diffractograms of 2d and 2e recorded at 80 °C and 120 °C, respectively, showed only one peak in the small-angle region, with no other significant features. By correlating the XRD information with the optical observations at the polarizing optical microscope, a hexagonal columnar phase could be assigned to the LC phases observed at higher temperatures on cooling from the isotropic state. For the calculation of the number of molecules per column unit, the following relations were used: N = Vcell/Vmol, where Vcell = Scolxh (assuming that h~4.5 Å, Scol = √3a2/2 and Vmol = Mw/(NA∙ρ); and Mw is the molecular weight, ρ is the density and it was approximated to 1 g∙cm−3 and NA is the Avogadro’ number). Given an interplanar distance of 25.44 Å (d100) for 2d, and 27.51 Å for 2e and the corresponding lattice parameter (a = 29.38 and 31.77 Å for 2d and 2e, respectively), then the discs are composed of two molecules of pyridinium salts having (N~2.23 and 2.15 for 2d and 2e, respectively), in total, eight alkyl chains at the periphery. The columnar organization can be regarded as the accumulation of two pyridinium cationic units which produces a disk-like arrangement with a parallel charge alternation to the normal of the 2D hexagonal lattice. In addition, the pyridinium salts with the highest number of carbon atoms (C122d and C142e) exhibited an additional mesophase at a lower temperature. While the POM observations showed a change of color but no significant textural modifications, the XRD patterns recorded at the lower temperature display a major transformation. The corresponding diffractogram of 2e recorded at 60 °C clearly display a series of five lines that can be indexed as d001, d002, d003, d004 and d007 of a lamellar organization. The sharpness of the small-angle peaks indicates the long range of the lamellar ordering and the 2D arrangement of the columns. No additional peak at higher angles that are correlated with the intracolumnar distances (~3.5 Å) could be observed, and, thus, a columnar lamellar organization with a certain degree of the disorder may be assumed for this LC phase [33,34,35,36]. In addition, the shift to a higher angle concomitant with the sharpening of the high-angle diffraction peak might indicate the closer molecular lateral packing of the molecules associated with columnar stacking within the layers [37,38].

4. Conclusions

Anion size and chain length variation for pyridinium salts 2ae and 3ae had a serious impact on mesophase stability and temperature range. On the contrary, these factors had little effect on the mesophase type. The pyridinium salts with the larger size PF6 counterion, 3ae, did not exhibit liquid crystal properties. The bromide salts required a minimum length of carbon chains to display their liquid crystalline properties. Thus, salts with shorter chains C6, C8 and C10 did not show mesophase, while longer chains analogues with C12 and C14 exhibited two enantiotropic columnar phases. The lower-temperature columnar phase was found to possess long-range lamellar organization based on the presence of a series of equidistant peaks in the low angle region of the XRD pattern. The C12 family of pyridinium salts with various counterions (Br, NO3, BF4 and PF6) reported earlier showed that only the bromide salt displayed mesomorphic behavior. Thus, the present work provides experimental evidence to confirm that the elongation of alkyl chains in these pyridinium salts is not enough to compensate for the destabilization of the mesophase by the inclusion of larger sized counterions.

Author Contributions

Conceptualization, V.C.; methodology, V.C., D.M.-M. and M.I.; validation, V.C., I.P., M.M. and T.S.; formal analysis, I.D., I.P. and F.L.C.; investigation, F.L.C., M.M., I.D. and M.I.; writing—original draft preparation, F.L.C. and V.C.; writing—review and editing, V.C.; supervision, V.C. All authors have read and agreed to the published version of the manuscript.

Funding

DMM acknowledges the support of the PubArt project.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Goossens, K.; Lava, K.; Bielawski, C.W.; Binnemans, K. Ionic liquid crystals: Versatile materials. Chem. Rev. 2016, 116, 4643–4807. [Google Scholar] [CrossRef] [PubMed]
  2. Chen, S.; Eichhorn, S.H. Ionic discotic liquid crystals. Israel J. Chem. 2012, 52, 830–843. [Google Scholar] [CrossRef]
  3. Dong, K.; Zhang, S. Hydrogen bonds: A structural insight into ionic liquids. Chem. Eur. J. 2012, 18, 2748–2761. [Google Scholar] [CrossRef] [PubMed]
  4. Hunt, P.A.; Ashworth, C.R.; Matthews, R.P. Hydrogen bonding in ionic liquids. Chem. Soc. Rev. 2015, 44, 1257–1288. [Google Scholar] [CrossRef]
  5. Ma, Y.; Liu, Y.; Su, H.; Wang, L.; Zhang, J. Relationship between hydrogen bond and viscosity for a series of pyridinium ionic liquids: Molecular dynamics and quantum chemistry. J. Mol. Liq. 2018, 255, 176–184. [Google Scholar] [CrossRef]
  6. Faul, C.F.J.; Antonietti, M. Ionic self-assembly: Facile synthesis of supramolecular materials. Adv. Mater. 2003, 15, 673–683. [Google Scholar] [CrossRef]
  7. Axenov, K.V.; Laschat, S. Thermotropic ionic liquid crystals. Materials 2011, 4, 206–259. [Google Scholar] [CrossRef]
  8. Fernandez, A.A.; Kouwer, P.H. Key developments in ionic liquid crystals. Int. J. Mol. Sci. 2016, 17, 731. [Google Scholar] [CrossRef][Green Version]
  9. Binnemans, K. Ionic liquid crystals. Chem. Rev. 2005, 105, 4148–4204. [Google Scholar] [CrossRef]
  10. Nelyubina, Y.V.; Shaplov, A.S.; Lozinskaya, E.I.; Buzin, M.I.; Vygodskii, Y.S. A new volume-based approach for predicting thermophysical behavior of ionic liquids and ionic liquid crystals. J. Am. Chem. Soc. 2016, 138, 10076–10079. [Google Scholar] [CrossRef]
  11. Neidhardt, M.M.; Wolfrum, M.; Beardsworth, S.; Wöhrle, T.; Frey, W.; Baro, A.; Stubenrauch, C.; Giesselmann, F.; Laschat, S. Tyrosine-based ionic liquid crystals: Switching from a smectic a to a columnar mesophase by exchange of the spherical counterion. Chem. Eur. J. 2016, 22, 16494–16504. [Google Scholar] [CrossRef] [PubMed]
  12. Cao, W.; Senthilkumar, B.; Causin, V.; Swamy, V.P.; Wang, Y.; Saielli, G. Influence of the ion size on the stability of the smectic phase of ionic liquid crystals. Soft Matter 2020, 16, 411–420. [Google Scholar] [CrossRef] [PubMed]
  13. Liu, S.; Yan, G.; Wang, J.; Zhou, J.; Bie, L.; Jia, Y.; Meng, F. Self-assembly, phase behaviour and ion-conducting property of pyridinium-based ionic liquid-crystalline oligomers. Liq. Cryst. 2021, 48, 201–214. [Google Scholar] [CrossRef]
  14. Wang, R.-T.; Tsai, S.-J.J.; Lee, G.-H.; Lai, C.K. Aggregation-induced emissions in columnar wedge-shaped pyridinium-based ionic liquid crystals. Dyes Pigments 2020, 173, 107913. [Google Scholar] [CrossRef]
  15. Tang, X.; Bai, L.; Kong, S.; Wang, X.; Meng, F. Multi-arm ionic liquid crystals formed by cholesteric mesophase and pyridinium groups. Liq. Cryst. 2019, 46, 1252–1265. [Google Scholar] [CrossRef]
  16. Jo, T.S.; Han, H.; Bhowmik, P.K.; Heinrich, B.; Donnio, B. Thermotropic liquid-crystalline and light-emitting properties of poly(pyridinium) salts containing various diamine connectors and hydrophilic macrocounterions. Polymers 2019, 11, 851. [Google Scholar] [CrossRef][Green Version]
  17. Wang, X.; Bai, L.; Kong, S.; Song, Y.; Meng, F. Star-shaped supramolecular ionic liquid crystals based on pyridinium salts. Liq. Cryst. 2019, 46, 512–522. [Google Scholar] [CrossRef]
  18. Ali, M.O.; Pociecha, D.; Wojciechowski, J.; Novozhilova, I.; Friedli, A.C.; Kaszyński, P. Highly quadrupolar derivatives of the [closo-B10H10]2-anion: Investigation of liquid crystalline polymorphism in an homologous series of 1,10-bis(4-alkoxypyridinium) zwitterions. J. Organomet. Chem. 2018, 865, 226–233. [Google Scholar] [CrossRef]
  19. Wang, R.-T.; Lee, G.-H.; Lai, C.K. Effect of counter ions on the mesogenic ionic: N–phenylpyridiniums. CrystEngComm 2018, 20, 2593–2607. [Google Scholar] [CrossRef]
  20. Luo, J.; Zhang, L.; Lu, J.; Bai, L.; He, X.; Meng, F. Polymerised ionic liquid crystals bearing imidazolium and bipyridinium groups. Liq. Cryst. 2017, 44, 1293–1305. [Google Scholar] [CrossRef]
  21. Zhao, D.; Zhang, L.; Bai, L.; Luo, J.; He, X.; Meng, F.-B. Synthesis and characterization of liquid-crystalline ionomers with pendant cholesteryl pyridinium salt mesogens. RSC Adv. 2016, 6, 26791–26799. [Google Scholar] [CrossRef]
  22. Bhowmik, P.K.; Al-Karawi, M.K.M.; Killarney, S.T.; Dizon, E.J.; Chang, A.; Kim, J.; Chen, S.L.; Principe, R.C.G.; Ho, A.; Han, H.; et al. Thermotropic liquid-crystalline and light-emitting properties of Bis(4-aalkoxyphenyl) viologen Bis(triflimide) salts. Molecules 2020, 25, 2435. [Google Scholar] [CrossRef] [PubMed]
  23. Kohnen, G.; Tosoni, M.; Tussetschläger, S.; Baro, A.; Laschat, S. Counterion effects on the mesomorphic properties of chiral imidazolium and pyridinium ionic liquids. Eur. J. Org. Chem. 2009, 32, 5601–5609. [Google Scholar] [CrossRef]
  24. Tosoni, M.; Laschat, S.; Baro, A. Synthesis of novel chiral ionic liquids and their phase behavior in mixtures with smectic and nematic liquid crystals. Helv. Chim. Acta 2004, 87, 2742–2749. [Google Scholar] [CrossRef]
  25. Kapernaum, N.; Lange, A.; Ebert, M.; Grunwald, M.A.; Haege, C.; Marino, S.; Zens, A.; Taubert, A.; Giesselmann, F.; Laschat, S. Current topics in ionic liquid crystals. ChemPlusChem 2022, 87, e2021003. [Google Scholar] [CrossRef] [PubMed]
  26. Cîrcu, V. Progress and Developments in Ionic Liquids; Handy, S., Ed.; IntechOpen: London, UK, 2017; pp. 285–311. [Google Scholar]
  27. Lu, J.T.; Lee, C.K.; Lin, I.J. Ionic liquid crystals derived from 4-hydroxypyridine. Soft Matter 2011, 7, 3491–3501. [Google Scholar] [CrossRef]
  28. Pana, A.; Badea, F.L.; Ilis, M.; Staicu, T.; Micutz, M.; Pasuk, I.; Cîrcu, V. Effect of counterion on the mesomorphic behavior and optical properties of columnar pyridinium ionic liquid crystals derived from 4-hydroxypyridine. J. Mol. Struct. 2015, 1083, 245–251. [Google Scholar] [CrossRef]
  29. Chiriac, L.F.; Pasuk, I.; Secu, M.; Micutz, M.; Cîrcu, V. Wide-range columnar and lamellar photoluminescent liquid-crystalline lanthanide complexes with mesogenic 4-pyridone derivatives. Chem. Eur. J. 2018, 24, 13512–13522. [Google Scholar] [CrossRef]
  30. Chiriac, F.L.; Iliş, M.; Madalan, A.; Manaila-Maximean, D.; Secu, M.; Cîrcu, V. Thermal and emission properties of a series of lanthanides complexes with N-biphenyl-alkylated-4-pyridone ligands: Crystal structure of a terbium complex with N-benzyl-4-pyridone. Molecules 2021, 26, 2017. [Google Scholar] [CrossRef]
  31. Pană, A.; Chiriac, F.L.; Secu, M.; Pasuk, I.; Ferbinteanu, M.; Micutz, M.; Cîrcu, V. A new class of thermotropic lanthanidomesogens: Eu(III) nitrate complexes with mesogenic 4-pyridone ligands. Dalton Trans. 2015, 44, 14196–14199. [Google Scholar] [CrossRef]
  32. Yoshio, M.; Ichikawa, T.; Shimura, H.; Kagata, T.; Hamasaki, A.; Mukai, T.; Ohno, H.; Kato, T. Columnar liquid-crystalline imidazolium salts. Effects of anions and cations on mesomorphic properties and ionic conductivities. Bull. Chem. Soc. Jpn. 2007, 80, 1836–1841. [Google Scholar] [CrossRef][Green Version]
  33. Cuerva, C.; Campo, J.A.; Cano, M.; Schmidt, R. Lamellar columnar liquid-crystalline mesophases as a 2D platform for anhydrous proton conduction. J. Mater. Chem. C 2019, 7, 10318–10330. [Google Scholar] [CrossRef]
  34. Veltri, L.; Maltese, V.; Auriemma, F.; Santillo, C.; Cospito, S.; la Deda, M.; Chidichimo, G.; Gabriele, B.; de Rosa, C.; Beneduci, A. Mesophase tuning in discotic dimers π-conjugated ionic liquid crystals through supramolecular interactions and the thermal history. Cryst. Growth Des. 2016, 16, 5646–5656. [Google Scholar] [CrossRef]
  35. Abe, Y.; Takagi, Y.; Nakamura, M.; Takeuchi, T.; Tanase, T.; Yokokawa, M.; Mukai, H.; Megumi, T.; Hachisuga, A.; Ohta, K. Structural, photophysical, and mesomorphic properties of luminescent platinum(II)-salen Schiff base complexes. Inorg. Chim. Acta 2012, 392, 254–260. [Google Scholar] [CrossRef]
  36. Malthete, J.; Nguyen, H.T.; Destrade, C. Phasmids and polycatenar mesogens. Liq. Cryst. 1993, 13, 171–187. [Google Scholar] [CrossRef]
  37. Choi, Y.-J.; Kim, D.-Y.; Park, M.; Yoon, W.-J.; Lee, Y.; Hwang, J.-K.; Chiang, Y.-W.; Kuo, S.-W.; Hsu, C.-H.; Jeong, K.-U. Self-assembled hierarchical superstructures from the benzene-1,3,5-tricarboxamide supramolecules for the fabrication of remote-controllable actuating and rewritable films. ACS Appl. Mater. Interfaces 2016, 8, 9490–9498. [Google Scholar] [CrossRef]
  38. Beneduci, A.; Cospito, S.; Crispini, A.; Gabriele, B.; Nicoletta, F.P.; Veltri, L.; Chidichimo, G. Switching from columnar to calamitic mesophases in a new class of rod-like thienoviologens. J. Mater. Chem. C 2013, 1, 2233–2240. [Google Scholar] [CrossRef]
Scheme 1. Preparation of the pyridinium salts discussed in this study.
Scheme 1. Preparation of the pyridinium salts discussed in this study.
Crystals 12 00715 sch001
Figure 1. Low field region of the 1H-NMR spectra of 2b (Br) and 3b (PF6).
Figure 1. Low field region of the 1H-NMR spectra of 2b (Br) and 3b (PF6).
Crystals 12 00715 g001
Figure 2. IR spectra (1500–500 cm−1 region) of 2e (Br) and 3e (PF6).
Figure 2. IR spectra (1500–500 cm−1 region) of 2e (Br) and 3e (PF6).
Crystals 12 00715 g002
Figure 3. Second heating-cooling DSC thermogram for 2b (a), 2e (b) and 3e (c).
Figure 3. Second heating-cooling DSC thermogram for 2b (a), 2e (b) and 3e (c).
Crystals 12 00715 g003
Figure 4. POM pictures for compound 2e at cooling from the isotropic liquid at 125 °C (a), 117 °C (the transition between the two columnar mesophases) (b), 55 °C (c).
Figure 4. POM pictures for compound 2e at cooling from the isotropic liquid at 125 °C (a), 117 °C (the transition between the two columnar mesophases) (b), 55 °C (c).
Crystals 12 00715 g004
Figure 5. XRD patterns of 2e at 120 °C (a) and at 50 °C (b).
Figure 5. XRD patterns of 2e at 120 °C (a) and at 50 °C (b).
Crystals 12 00715 g005
Table 1. Transition temperatures (in °C) and enthalpies (kJ/mol) for the pyridinium salts.
Table 1. Transition temperatures (in °C) and enthalpies (kJ/mol) for the pyridinium salts.
CompoundHeating/Cooling Scans
2aCr 31 (6.7) Iso
2bCr 38 (3.7) Iso-12 g
2cCr 60 (74.3) Iso 9 (13.8) Cr
2dCr 62 (88.1) Col 108 (0.9) Iso 105 (0.9) Col 74 (1.4) LCol 23 (18.2) Cr
2eCr1 73 (136) LCol 125 (0.3) Col 130 (0.4) Iso 129 (0.3) Col 118 (0.3) LCol 31 (37.4) Cr2 14 (4.5) Cr1
3aCr 46 (15.9) Iso-9 g
3bCr 48 (21.0) Iso-4 g
3cCr1 52 (0.4) Cr2 61 (116.6) Iso 2 (7.1) Cr1
3dCr 72 (80.5) Iso 26 (35.2) Cr
3eCr1 81 (63.4) Cr2 87 (36.3) Iso 56 (63.1) Cr2
The corresponding enthalpies are given in parenthesis: Cr1; Cr2—crystalline phases; g—glassy state; Iso—isotropic phase; Col—columnar phase; LCol—lamello-columnar phase.
Table 2. XRD data for bromide salts 2d and 2e.
Table 2. XRD data for bromide salts 2d and 2e.
CompoundMesophaseT/°CIndexationD-Spacing obs./ÅD-Spacing calc./ÅLattice Parameters/Å b
2dCol8010025.4425.44a = 29.38
Broad c4.5
2eCol120 a10027.5127.51a = 31.77
///Broad c4.5//
/LCol6000139.7639.76/
///00219.7519.88/
///00313.1213.25/
///0049.849.94/
///0075.625.68/
///Broad c4.3//
a On cooling from isotropic state. b The hexagonal columnar lattice parameter a = 2<d100>/√3.c Broad peak assigned to molten alkyl chains.
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Dumitru, I.; Chiriac, F.L.; Ilis, M.; Pasuk, I.; Manaila-Maximean, D.; Micutz, M.; Staicu, T.; Cîrcu, V. Evidence of Counterion Size Effect on the Stability of Columnar Phase of Ionic Liquid Crystals Based on Pyridinium Salts Derived from N-3,4,5-Tri(alkyloxy)-benzyl-4-pyridones. Crystals 2022, 12, 715. https://doi.org/10.3390/cryst12050715

AMA Style

Dumitru I, Chiriac FL, Ilis M, Pasuk I, Manaila-Maximean D, Micutz M, Staicu T, Cîrcu V. Evidence of Counterion Size Effect on the Stability of Columnar Phase of Ionic Liquid Crystals Based on Pyridinium Salts Derived from N-3,4,5-Tri(alkyloxy)-benzyl-4-pyridones. Crystals. 2022; 12(5):715. https://doi.org/10.3390/cryst12050715

Chicago/Turabian Style

Dumitru, Isabela, Florentina L. Chiriac, Monica Ilis, Iuliana Pasuk, Doina Manaila-Maximean, Marin Micutz, Teodora Staicu, and Viorel Cîrcu. 2022. "Evidence of Counterion Size Effect on the Stability of Columnar Phase of Ionic Liquid Crystals Based on Pyridinium Salts Derived from N-3,4,5-Tri(alkyloxy)-benzyl-4-pyridones" Crystals 12, no. 5: 715. https://doi.org/10.3390/cryst12050715

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