Mohamed
Alaasar
*ab,
Marko
Prehm
a,
Marcel
Brautzsch
a and
Carsten
Tschierske
*a
aInstitute of Chemistry, Martin Luther University Halle-Wittenberg, Kurt Mothes Str. 2, D-06120 Halle (Saale), Germany. E-mail: carsten.tschierske@chemie.uni-halle.de
bDepartment of Chemistry, Faculty of Science, Cairo University, Giza, Egypt. E-mail: malaasar@sci.cu.edu.eg
First published on 9th June 2014
Stochastic achiral symmetry breaking in soft matter systems, leading to conglomerates of macroscopically chiral domains (so-called dark conglomerate = DC phases) is of contemporary interest from a fundamental scientific point of view as well as for numerous potential applications in chirality sensing and non-centrosymmetric materials. Herein we report the synthesis and investigation of first azobenzene containing bent-core mesogens derived from 4-methylresorcinol forming DC phases with a new structure, distinct from the known fluid sponge-like distorted smectic phases as well as from the helical nano-filament phases (HNF phases, B4 phases). The effects of chain length and other structural modifications on achiral symmetry breaking were investigated. Homologues with relatively short alkyl chains form achiral intercalated lamellar LC phases (B6 phases), but on increasing the chains, these are replaced by the chiral and optically isotropic DC phases. Compounds with the longest alkyl chains form low birefringent crystalline conglomerates which represent less distorted versions of the optically isotropic DC-phases. Introducing additional peripheral substituents at both outer rings removes the DC phases. The DC phases were also removed and replaced by modulated smectic phases if the azo groups were replaced by ester units, showing that azo groups favour DC phase formation with new nanostructures, distinct from the previously known types.
Interestingly, almost all of the known BCLCs with HNF phases incorporate the hydrolytically unstable benzylideneaniline (Schiff base) moiety with the exception of only very few recent examples.26–28 This calls for new materials with DC phases, showing enhanced chemical stability and providing new phase sequences involving the HNF phases. A broader variety of different molecular structures could also lead to an improved understanding of the molecular structural factors governing the formation of distinct subtypes of DC phases, thus providing rules for the directed design of such materials.
BCLCs incorporating azo (–NN–) linkages represent versatile materials due to their photochromic effects in addition to high birefringence and high polarizability, leading to significant nonlinear optical activity.6,29,30 The cis–trans isomerisation of the azo linkage in the presence of UV light could be used, for example, in high-density data storage systems, for sensors, photonic switches and molecular logic gates.31 Though a variety of azobenzene based BCLCs with interesting properties have been reported,29,32–34 until recently no such BCLCs with DC phases have been available; only bent dimesogens combining two rod-like azobenzene units via an odd-numbered alkylene spacer were reported.27 We have found that iodine28 or bromine34a substitution in 4-position at the bent central resorcinol unit of azobenzene based BCLCs leads to a new type of DC-phases (Scheme 1).28 Hence, it appears that the size of the halogens is of importance. Bulky halogen atoms like bromine (cv = 0.33 nm3)35 or iodine (cv = 0.45 nm3),35 seem to be favourable for formation of DC phases, whereas no DC phases were found for BCLC with hydrogen32e or smaller halogens in the same position (see Scheme 1; F: cv = 0.13 nm3; Cl: cv = 0.27 nm3).34,35 Hence, the question arose if azobenzene BCLCs with other bulky groups at the bent core, having a size comparable to iodine/bromine, could also lead to azobenzene based BCLCs showing DC phases. The methyl group has a size (cv = 0.32 nm3)35 comparable to bromine but it is almost non-polar in contrast to the C-halogen bonds which introduce a significant dipole moment.
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Scheme 1 LC phases found for 4-halogenoresorcinol based bent-core mesogens with azobenzene wings (abbreviations: Cr = crystalline solid, USmC = undulated smectic phase; N = nematic phase, B6 = intercalated smectic phase formed by ribbons with only short range register; DC = dark conglomerate phase; phases in brackets were observed only for one homologue in a small temperature range).28,34a |
Here we report a series of new BCLCs derived from 4-methylresorcinol36,37 possessing two azobenzene side arms (An, see Scheme 2). These compounds show B6 phases if the terminal chains are short and a new type of dark conglomerate phases if the chains are sufficiently long. Besides these isotropic DC phases also a birefringent crystalline conglomerate was observed for a long chain compound. The formation of this phase depends on the applied cooling rates and the transition between the isotropic and birefringent types of conglomerate phases was studied. In addition, the effect of lateral groups X (see Scheme 2, X = F, Br, CH3) at the outer rings of these BCLCs (compounds Bn, C14 and D14, respectively) has been investigated. The phase behaviour of these new compounds is compared with related compounds incorporating terephthalate or benzoate based wing groups instead of the azobenzenes, either reported in the literature36 or synthesized herein (E14, F14 and G14 see Section 3.6).
DFT computation was carried out with the Gaussian 09 package.38 Geometry optimization was performed with the B3LYP functional and the LAN L2 DZ basis set. The solvation model was IEFPCM with solvent chlorobenzene.
Comp. | n | X | Heating | Cooling |
---|---|---|---|---|
a Before measurement the compounds were melted and heated to 150 °C to remove traces of enclosed solvent, afterwards they were cooled with 10 K min−1 to room temperature; the phase transition temperatures (peak temperatures) were taken from the following heating and cooling scans at 10 K min−1, if not otherwise specified; abbreviations: SmC = synclinic tilted birefringent smectic phase; SmCaPA = anticlinic tilted antiferroelectric SmC phase; Iso = isotropic liquid; Cr[*] = crystalline phase composed of a conglomerate of chiral domains, for other explanations, see Scheme 1. b Obtained on heating after previous cooling to 75 °C with 10 K min−1. c Obtained on heating after previous cooling to 80 °C with 20 K min−1. d Total enthalpy for both transitions. e Obtained on heating after previous cooling to 80 °C with 2 K min−1. f The actual phase sequence strongly depending on conditions, see DSC traces in Fig. 2b; transition enthalpy value could not be determined for the B6-DC transition (see Section 3.3). g Cooling with 2 K min−1. h Partial crystallization. | ||||
A6 | 6 | H | Cr 124 [41.0] B6 131 [11.9] Iso | Iso 129 [12.3] B6 |
A8 | 8 | H | Cr 111 [35.9] Iso | Iso 96 [11.1] B6 62 [9.1] Cr |
A9 | 9 | H | Cr 110 [37.4] Iso DC 100 [22.7] Isob | Iso 87 [9.4] B6 67 [16.5] Crf Iso 87 [9.4] B6 ∼ 85 DC [≥9.1] 67 Crf |
A10 | 10 | H | Cr 107 [37.4] Iso DC 100 [25.5] Isoc | Iso 87 [24.1] DC |
A12 | 12 | H | Cr 109 [38.1] Iso DC 102 [27.3] Isob | Iso 87 [26.8] DC |
A14 | 14 | H | DC 101 [31.4] Iso | Iso 88 [33.9] DC |
A16 | 16 | H | DC 102 [40.8] Iso | Iso 90 [43.9] DC |
A18 | 18 | H | DC 103 [49.6] Iso | Iso 93 [51.7] DC |
A20 | 20 | H | Cr[*] 99 DC 104 [68.0]d Iso DC 104 [56.7] Isoe | Iso 92 [70.8] Cr[*] Iso 95 [59.0] DCg |
A22 | 22 | H | Cr[*] 105 [73.2] Iso | Iso 96 [76.5] Cr[*] |
B6 | 6 | F | Cr 112 [41.3] Iso | Iso 88 [8.6] SmCaPA 67 [10.5] Crh |
B14 | 14 | F | Cr 90 [32.9] SmCaPA 95 [12.8] Iso | Iso 90 [15.2] SmCaPA 74 [39.8] Cr |
B20 | 20 | F | Cr 95 [93.0] Iso | Iso 92 [16.0] SmCaPA 82 [77.7] Cr |
C14 | 14 | Br | Cr 78 [77.2] Iso | Iso 30 [53.2] Cr |
D14 | 14 | CH3 | Cr 79 [47.9] Iso | Iso 33 [0.9] SmC < 20 Cr |
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Fig. 1 Compound A6. (a) Texture (crossed polarizers) as observed for the B6 phase at T = 120 °C (on cooling, textures observed after applying shear stress are shown in Fig. S2†); (b) XRD pattern of an aligned sample of the B6-phase at 80 °C; (c) 2θ-scan over this pattern and (d) the proposed model of the molecular organization in the B6 phase, left: view along the bending direction, right: side view perpendicular to the molecular bending plane (in this direction the ribbons are quasi infinite) and the assumed electron density modulation profile in the middle.41 |
The XRD pattern (Fig. 1b and c) shows only one sharp peak in the small angle region corresponding to a d-value of 2.0 nm (T = 80 °C), which is smaller than half of the molecular length (Lmol) in a conformation with a 120° bent aromatic unit and the alkyl chains in the most stretched all-trans conformation. For compound A6Lmol is between 4.3 and 4.5 nm, depending on the assumed conformation shown in Fig. S1.† This confirms the intercalated B6-type smectic phase deduced from optical investigations. According to the present understanding, this is a frustrated smectic phase with layers broken into ribbons and adopting a staggered organization with only short range periodicity between the ribbons (see Fig. 1d); the layer frustration takes place in the direction perpendicular to the molecular bending plane (Fig. 1d).39,40
The wide angle scattering is diffuse and has a maximum at 0.43 nm, in line with the LC state of this phase. For an aligned sample this scattering is split into four maxima indicating the presence of a tilt of about 26° (Fig. 1b and S12†). This tilt could arise either from a tilt of the molecular bending planes, or alternatively, from the inherently tilted orientation of the individual rod-like wings of the bent-core mesogens, similar to anticlinic SmC phases.41 The latter would be in line with recent microbeam XRD results obtained for B6 phases of Schiff base compounds.39a In this case the orientation of the molecules would be on average orthogonal and the splitting is related to the angle of the molecular bent of 128° which is in good agreement with the geometry provided by the molecular structure. This would also be in line with the optical textures which have the extinction brushes strictly parallel to the polarizers (see Fig. 1a). However, the measured d value is a bit shorter than half the molecular length (2d/Lmol ∼ 0.9) which in this case must be attributed to partial intercalation and conformational disorder of the alkyl chains. On cooling A6 from the isotropic state the B6 phase appears at T = 129 °C and remains on cooling down to room temperature without visible crystallization of the sample (for DSC traces, see Fig. 2a), but the sample becomes glass-like solid without any change of the texture at ∼40 °C. This might indicate a transition to a glassy state of the B6 phase or an isomorphous crystallization. As no clear DSC peak (only a small hump between 40 and 50 °C, see Fig. 2a) was observed in the cooling traces and crystallization is observed >35 °C on heating, a glassy B6 phase (gB6) appears more likely.
In electrooptical investigations using a triangular wave voltage no current peak could be observed in the whole temperature range of this mesophase up to a voltage of 200 Vpp in a 6 μm ITO cell. These observations, together with the relatively high transition enthalpy value of ΔH = 12.3 kJ mol−1 for the Iso–LC transition at T = 129 °C are in line with the suggested B6 phase. With increasing chain length (n = 8 and 9) the B6 phase is retained but the Iso–B6 transition temperature decreases to 96 °C for A8 and to 87 °C for A9, and the B6 phase becomes monotropic (metastable) for these two compounds.
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Fig. 3 Optical micrographs observed for A9 between crossed polarizers: (a) B6 phase at T = 86 °C; (b) growth of the DC phase and the birefringent crystalline phase from the B6 phase; (c) DC phase as grown from B6 (T = 83 °C, different region) after rotating one polarizer by 10° from the crossed position in the anticlockwise direction and (d) in the clockwise direction, showing the chiral domains (on a larger field of view the stochastically distributed chiral domains occupy equal areas); the texture related to (c), (d), but between 90° crossed polarizers is shown in Fig. S3b†; additional textures are shown in Fig. S3a, c and d.† |
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Fig. 4 a–d) Growth of the circular chiral domains of the DC phase of A10 upon cooling from the isotropic liquid state at T = 87 °C as observed between slightly uncrossed polarizers (see arrows); the textures of the DC phase of A14 are shown in Fig. S4.† |
The melting of the DC phases (DC–Iso-transition) takes place around 100–104 °C and the crystallization of the DC phase (Iso–DC transition) is found between 87 and 95 °C for all compounds A10–A20 and both transition temperatures increase slightly with rising alkyl chain length (see Table 1 and Fig. 5a). Hence, there is a supercooling of this phase transition by about 10 K (peak temperatures at scanning rates of 10 K min−1). The formation of the DC phases is associated with relatively high transition enthalpies, ranging between ΔH ∼ 24 and 59 kJ mol−1 (measured in cooling scans), strongly rising with growing alkyl chain length from A10 to A20 (see Table 1 and Fig. 5a).
Compounds A10 and A12 easily crystallize on cooling or on reheating, but the DC phases of compounds with longer chains (n = 14–20) do not crystallize, once the DC phase is formed, as shown in Fig. 5b for compound A18 as an example (for additional DSC curves, see Fig. S7 and S8). In the case of the long chain compound A20 a different behaviour is observed which is discussed here in some more detail. For this compound there is a strong effect of the cooling rate on the phase sequence and the phase structure (see Fig. 5c and d). On cooling from the isotropic liquid phase with a low rate of ≤2 K min−1 (Fig. 5c, curve b) the DC phase is formed at T = 95 °C and it does not crystallize on further cooling, and on heating only a single peak is observed at T = 104 °C (Fig. 5c, curve a), similar to compounds A14–A18 (Fig. 5b). The transition enthalpy is ∼57 kJ mol−1 on heating and ∼59 kJ mol−1 on cooling. However, on cooling with a faster rate of ≥5 K min−1 (Fig. 5d, curve d) a crystalline phase with a weakly birefringent spherulitic texture (see Fig. 6b) is formed at T = 92 °C and the transition enthalpy is now significantly larger, around ∼71 kJ mol−1 on cooling.44 The spherulitic texture (Fig. 6b) is similar to those found for columnar or (modulated) smectic LC phases, however, this phase is solid-like and does not flow on applying shear forces, and therefore, this is a crystalline phase.
Interestingly, also this crystalline phase is chiral and composed of domains with opposite handedness, i.e. dark and bright domains become visible if the polarizers are slightly uncrossed (see Fig. 6a and c), hence, this birefringent conglomerate phase is assigned as Cr[*]. Each of the spherulites appears to have uniform chirality, so it seems that the chirality is determined by each nucleus and is preserved through the growth process.45 On further cooling the Cr[*] phase is retained and does not change down to room temperature, but on heating to T = 99 °C it transforms into the DC phase. At this transition the spherulitic texture becomes uniformly isotropic and the chirality as well as the sign of chirality in the distinct domains is retained (see Fig. 6e–g). This temperature corresponds to the position of the exotherm II in the heating curve c in Fig. 5d. The unusual shape of the DSC heating curve c is characterized by a significant tailing which rises up to a local maximum I, before it abruptly goes through an exothem II, and finally the peak maximum III is reached. This kind of DCS curve is always found for the heating curves after cooling the sample with rates ≥5 K min−1, independent of the used heating rates (see Fig. S9†). The endothermic tailing I, starting at T ∼ 85 °C, is interpreted as a result of a chain melting process which leads to a softening of the Cr[*] phase. This obviously allows a denser packing (crystallization) of other molecular parts, giving rise to the exotherm II in the heating curve. At this temperature the Cr[*] phase transforms into the DC phase, i.e. this transition is accompanied by a layer deformation which leads to the formation of the optically isotropic DC phase at T = 99 °C. On further heating this DC phase melts into the isotropic liquid at the endothermic peak III at T = 104 °C. Once formed (either on cooling the preformed DC phase or on slow cooling from the isotropic liquid sate), the DC phase is stable and it is retained down to room temperature; only a single peak at T = 104 °C is observed on heating (curve e in Fig. 5d). Even after storage at room temperature for more than 8 weeks the same transition temperatures and enthalpies were obtained. The persistence of the DC phases might be the result of the freezing of disordered alkyl chain segments into an immobilized, probably a glassy state, which, once formed, inhibits the transformation into the chiral Cr[*] phase or any other crystalline phase.
Compound A22 with the longest chains is a crystalline solid with a melting point at T = 105 °C. No formation of a DC phase could be detected at any cooling rate. Also in this case the crystalline phase formed on cooling consists of a conglomerate of chiral crystals (see Fig. S5†), though the chiral domains cannot be observed with the same clarity as for A20, because the birefringence is higher and no uniform texture is obtained. In the following focus is on the DC phases of compounds A10–A20.
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Fig. 7 XRD pattern of the DC phase of compound A14 at T = 70 °C, (a) complete diffraction pattern, (b) small angle region and (c) 2θ-scans at T = 70 °C and T = 90 °C. |
In all cases the d-value is significantly larger than Lmol/2, but also smaller than the single molecular length, indicating a tilted monolayer-like organization of the molecules in the DC phases. The d-value of the layer reflection grows, as expected, with rising molecular length (Fig. 9a). The ratio d/Lmol is ∼0.73–0.75 for all investigated compounds which would, according to d/Lmol = cosβ, lead to a tilt angle around 40°.46 This relatively large difference between d and Lmol distinguishes these DC phases from the previously reported HNF phases where d is usually close to the molecular length.16,17
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Fig. 9 Dependence of the XRD reflex position in the DC phases of compounds A10–A20 on chain length, (a) d-values of the layer reflections with the observed higher harmonics and (b) wide angle scattering maxima, the assignment of the reflections is shown in Fig. 7c, see also Fig. S13–S17.† |
In the medium angle region of the diffraction patterns of compounds A14–A20 there are additional distinct scattering maxima on top of a broad diffuse scattering covering the range between 2θ = 5° and 2θ = 15° (see Fig. 8), only for A10 exclusively the diffuse scattering could be observed. These reflections can be indexed as higher harmonics of the layer reflection (see Fig. 7c), as also found for the HNF phases. In the wide angle range there is a broad feature which could be fitted to 4 maxima (w1–w4) in the 2θ range between 19 and 21° (see Fig. 7c). This pattern excludes fluid sponge phases, showing exclusively a very diffuse wide angle scattering besides the layer reflection. However, it is also distinct from the typical patterns of HNF phases (B4 phases), where the wide angle reflections have other positions and appear as significantly sharper separate peaks.9,20,21
With growing chain length the intensity of the second harmonics of the small angle scattering decreases and it has completely disappeared for compound A18 (Fig. 8), whereas the (50) and (40) reflections increase in intensity, most probably due to the changing electron density modulation resulting from the changing thickness of the aliphatic layers and other structural modifications. There is also a nearly continuous change of the positions of the wide angle scattering (Fig. 8 and 9), indicating continuous structural transformations depending on the chain lengths. An indexing of the wide angle diffraction patterns was not attempted, because of the limited number and the diffuse character of the reflections. Due to the overlapping of several scattering maxima the precise assignment of the positions of the maxima is difficult and the presence of additional scattering in this region cannot be excluded. In any case, the scattering in this region should result from the packing of the crystallized (mainly aromatic) segments on a 2D in-plane lattice. The significant line broadening is thought to be due to the limited correlation length of the crystalline micro-domains.
Major changes can be observed for the scattering w3 occurring around 2θ ∼ 19–20° which decreases in intensity (compare Fig. 8a–e) and is shifted to smaller d-values (see Fig. 9b) from A14 to A20. Based on its d-value in the range between 0.46 and 0.43 nm and its strong intensity dependence on temperature (see discussions below) it is thought that this scattering is most likely due to the mean distance between less ordered (not crystallized) segments of the alkyl chains. The observation that with increasing chain length the position of w3 is shifted to smaller d-values would be in line with a denser chain packing for longer chains.
The temperature effect on the XRD pattern of compound A14 in the DC phase is shown in Fig. 7c. There is no significant influence on the intensities and positions of the scattering maxima with exception of w3 which is strongly reduced at decreased temperature, though its position is retained. Reducing the temperature has obviously a similar effect on the intensity of this scattering like increasing the alkyl chain length. This supports the assumption that this scattering maximum does not belong to the 2D in-plane lattice and could be attributed to the mean distance between the disordered alkyl chain segments. The fraction of the more disordered alkyl chain segments becomes smaller as temperature is reduced and as the alkyl chain length is increased, because longer chains provide a higher tendency for chain crystallization, as mentioned above. This corresponds with the observed strong rise of the DC-Iso transition enthalpy from 24.1 kJ mol−1 for A/10 to 59 kJ mol−1 for A/20 (see Table 1 and Fig. 5a; values on heating). In line with increasing chain crystallization by chain elongation, the optically isotropic DC phase of compound A20 is in competition with a low birefringent crystalline conglomerate phase Cr[*] and exclusively a Cr[*] phase is formed by A22 with the longest chains.
For compound A20 the XRD patterns were recorded at the same temperature (T = 90 °C) after slow cooling (0.5 K min−1Fig. 8e) in the DC phase as well as after fast cooling (10 K min−1Fig. 8f) in the Cr[*] phase. Surprisingly, the two XRD patterns look very similar, only all scattering appear to be a bit broader and have slightly lower intensity in the birefringent Cr[*] phase, though the sample and exposure time were identical. This is reproducibly observed and would suggest a reduced local order in the Cr[*] phase compared to the DC phase. This is in line with the suggested core crystallization as origin of the exotherm (II) occurring on heating at the transition from the birefringent Cr[*] phase to the optically isotropic DC phase (see curve c in Fig. 5d). Because chirality is observed in the birefringent Cr[*] phase as well as in the isotropic DC phase, the aromatic cores should in both phases adopt chiral helical conformations with uniform helix sense, which is opposite in the distinct chiral domains. At the Cr[*]–DC transition the contrast between the dark and bright domains decreases (compare Fig. 6a, e and c, g). This reduced optical activity indicates a reduction of the helical twist of the molecular conformations at the transition from the crystalline to the DC phase. Molecular entities with uniform helix sense cannot be densely packed in nondistorted layers and thus induce twist and curvature. This distortion increases with growing packing density of the helical entities, and therefore the denser core packing leads to a stronger layer deformation force, giving rise to the formation of the optically isotropic DC phase. The birefringent Cr[*] phase, formed on rapid cooling appears to be dominated by optimized alkyl chain packing (chain crystallization), which allows a non-twisted lamellar or modulated lamellar organization of the molecules, but without optimized core-packing. The aromatic cores remain in a strongly twisted helical conformation, leading to a high optical activity, but the strong molecular twist also leads to a disruption of the aromatic layers into smaller domains (see Fig. 6d). Upon heating the Cr[*] phase, the alkyl chain order decreases and a growing fraction of these chains becomes disordered. This allows a denser core packing, simultaneously leading to a reduced helicity of the molecular conformations (reduced optical activity) and, giving rise to a strong layer distortion and formation of the DC phase with an increased alkyl chain disorder. This means that the isotropic DC phases are the result of the optimization of core packing and represent disordered versions of the birefringent crystalline conglomerates (Cr[*] phases), providing improved alkyl chain packing. With rising alkyl chain length the chain crystallization becomes increasingly more important. For compound A20 formation of the optical isotropic DC phase can still be achieved by using sufficiently slow cooling rates, so that the slow core crystallization can take place and determine the structure, leading to the DC phase. On fast cooling, however, densest core packing obviously cannot be achieved and the fast chain crystallization leads to a non-twisted lamellar organization, giving rise to the birefringent conglomerate phase Cr[*] with reduced core order and enhanced optical activity. For compound A22 chain crystallization dominates at all cooling rates, and hence, exclusively a crystalline phase is formed.
Low birefringent crystalline conglomerate phases were also observed for compounds A14–A18, but for these compounds very high cooling rates (≫20 K min−1) are required for their formation and there is apparently always a coexistence of these birefringent Cr[*] phases with the isotropic DC phases, which makes the investigations difficult. Fig. 10 shows representative textures and DSC curves as obtained for compound A16 after rapid cooling (30 K min−1 for the texture and 50 K min−1 before recording the DSC trace a). For these compounds core crystallization is sufficiently fast compared to alkyl chain crystallization and therefore DC phases can be observed for moderate cooling rates. The Cr[*] phases are absent for all shorter homologues starting with A12, which have the smallest contribution of alkyl chain crystallization to the total transition enthalpy value (Fig. 5a); here self-assembly is dominated by optimized core packing, which leads to DC phase formation.
Mixture | Heating T/°C | Cooling T/°C |
---|---|---|
a Transition temperatures were taken from the observed textures using polarized optical microscopy; abbreviations: N = nematic phase, for other abbreviations please see Table 1. | ||
A14–5-CB | Cr1 39 Cr2 85 Iso | Iso 54 N 53 Cr |
A16–5-CB | Cr 64 DC 73 Iso | Iso 66 DC |
A18–5-CB | DC 77 Iso | Iso 72 DC |
A20–5-CB | DC 80 Iso | Iso 78 DC |
A22–5-CB | Cr[*] 59 DC 87 Iso | Iso 80 DC 37 Cr[*] |
B14–5-CB | Cr 63 Iso | Iso 61 Cr |
The longer compounds A16–A20 behave differently; for the 1:
1 mixtures the DC phases were retained and their temperature ranges increase with growing chain length (Table 2 and Fig. S20†). However, at only slightly higher 5-CB concentration, as for example, in the 4
:
6 mixtures of compounds A16–A20 with 5-CB the chiral DC phase is lost and instead a heterogenous mixture is obtained indicating that the amount of 5-CB which can be mixed into the DC phases of compounds An is strongly limited. So, compared with the HNF phases, the DC phases of compounds An can only be retained if the alkyl chains are sufficiently long, but also in this case much less 5-CB is tolerated. These observations, in conjunction with the XRD studies, confirm that the DC phases of compounds An should be different from the classical HNF phases. It appears that these phases are formed by smaller nano-domains instead of long helical filaments, in line with the results discussed in the previous sections. Because no extended filaments are formed, no gel-like networks of these fibers are possible and therefore these compounds can take up only a limited amount of 5-CB, which is directly incorporated between the bent-core molecules thus reducing the stability of the DC phases.
Mixing the longest homologue A22, which does not show any DC phase, with 5-CB in 1:
1 ratio induces a DC phase as an enantiotropic phase between T = 59 °C and 87 °C (see Fig. S21†). This shows that 5-CB can reduce the chain crystallization and thus allow the formation of the DC phase even if the pure compound itself does not show any DC phase. However, no DC phase can be induced in the fluorinated compounds Bn (X = F, 1
:
1 mixtures with 5-CB) that show polar smectic phases and are discussed in Section 3.5.
Replacing the fluorine substituents in Bn by methyl groups (D14) leads to a monotropic SmC phase (for texture see Fig. S6b†) without polar order, also indicated by the much smaller SmC–Iso transition enthalpy values (0.9 kJ mol−1) and the observation that no current peak could be observed up to a voltage of 200 Vpp in a 6 μm ITO cell. It appears that increasing the size of the peripheral substituents X reduces the packing density significantly, thus leading to strong reduction of mesophase stability in the order H ∼ F > CH3 > Br, at first leading to a loss of polar order for X = CH3 and finally to a complete suppression of all mesophases for X = Br. As the electronegative F atoms increase the polarity of the core region, and hence increase the segregation of the core from the lipophilic alkyl chains, there is no significant mesophase destabilization or a slight stabilization if H is replaced by F (compare A14 and B14 in Table 1). But nevertheless, chiral segregation is removed. The dominance of steric effects of Br and CH3 leads to the loss of polar order and to the lowest LC phase stability for these compounds.
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Scheme 3 Chemical structures of the synthesized 4-methylresorcinol based terephthalates E14, F14 and benzoate G14 with transition temperatures (T/°C) and corresponding enthalpies (ΔH/kJ mol−1, given in square brackets) on heating (top lines) and cooling (bottom lines, both recorded at a rate of 10 K min−1); abbreviations: Sm![]() ![]() |
In XRD measurements of compound E14 (Fig. S18†) several equally spaced sharp reflections can be found in the small angle region, indicating a lamellar structure with a d-value of 4.83 nm. The diffuse scattering in the wide angle region shows four intensity maxima beside the equator, from which a tilt angle of the molecules of ∼28° could be calculated. As the extinction crosses are approximately parallel to the polarizers (Fig. S6c†) and an equal intensity of the wide angle scattering is found (Fig. S18a and b†) the tilt correlation should be anticlinic. Though there are indications of layer modulations or undulations from other experimental data, these are not visible in the XRD patterns. Either the modulation wavelength is very long, so that the layer reflections are not resolved into separate reflections, or the reflections with h and k ≠ 0 are too weak to be detected with the used XRD setup.
Replacing the terminal alkoxy chains in E14 by alkyl chains in compound F14 (see Scheme 3, for DSC traces see Fig. S11a†) leads to a compound with about 20 K lower clearing temperature which can also be assigned as SmaPA based on the observed textures and measured Ps values (Ps = 300 nC cm−2 at 95 °C, see Fig. S24†). The major difference between the two compounds is the inclination of the dark extinctions upon applying an electric field (Fig. S25†), indicating that the switching process in this case takes place on a cone; so probably the modulation wavelength of F14 is larger than for E14.
Inverting the direction of the terminal ester group in compound G14 (see Scheme 3) further reduces the transition temperatures, which are now similar to those of the azobenzene derivative A14 (for DSC traces see Fig. S11b†). Also in this case the texture is similar to those of some modulated smectic phases (Fig. S6d†). The position of the extinction crosses is inclined with the orientation of the polarizers and thus indicates a synclinic tilted organization of the molecules. In electrooptic studies (160 Vpp in a 6 μm ITO cell) no current response can be detected. This might be due to a shorter modulation wavelength than in the case of E14, which is known to suppress polar switching or would require very high voltages. Also the observation of a uniform synclinic tilt would be in line with a B1rev-like modulated SmC phase with an oblique lattice. However, it was not possible to further confirm the proposed phase structure by XRD due to the rapid crystallization. Overall, replacing the azobenzene wings by terephthalates (E14, F14) or benzoates (G14) removes the DC phases and leads to polar and apolar smectic phases with a significant tendency for layer modulation or undulation.
Introduction of additional substituents at the outer rings of the bent-core molecules An removes the DC phases and replaces them first by polar smectic phases (X = F, SmCaPA). Upon further enlargement of these substituents (X = CH3) also polar order is removed, yielding a non-polar SmC phase which is then removed for the compound with the largest substituent X = Br. Replacing the azo groups by ester groups in the related terephthalates or benzoates also removes the DC phases and leads to different types of modulated SmC phases which in most cases show polar switching.
Overall, new modifications of isotropic as well as birefringent conglomerate phases were observed and the relationship between molecular structure and formation of these phases was identified. It appears that the azobenzene unit is a specially powerful tool for introducing new types of chiral conglomerate phases, distinct from the typical B4 type phases found for benzylidene imines. There seems to be a whole zoo of different types of these DC phases, ranging from the fluid B2-like sponge phases to several distinct types of soft crystalline phases, including modulated subtypes;49–51 obviously only a small fraction of the potential structures has been explored yet. Moreover, the possibilities provided by introduction of the photoisomerizable azobenzene units into BCLC forming DC phases could lead to interesting perspectives for chirality switching and phase modulation, leading to unique and potentially useful multifunctional chiral materials for application in chiral discrimination of chiral physical forces and molecular species22 and as non-centrosymmetric materials.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c4tc00533c |
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