Tobias
Wöhrle
a,
Stuart James
Beardsworth
a,
Christopher
Schilling
a,
Angelika
Baro
a,
Frank
Giesselmann
b and
Sabine
Laschat
*a
aInstitut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany. E-mail: sabine.laschat@oc.uni-stuttgart.de
bInstitut für Physikalische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
First published on 4th March 2016
Triphenylbenzenes with different substitution patterns at the outer phenyl rings have been successfully synthesised. Sixfold n-alkoxy substitution was insufficient for mesomorphism, but already increasing the number of side chains by three methoxy groups led to liquid crystalline behaviour and mesophase formation. Symmetrical triphenylbenzenes with nine n-alkoxy side chains (≥C9) formed broad enantiotropic mesophases. The symmetry of the liquid crystalline phases was unambiguously determined by X-ray diffraction measurements as Colh and Colho for symmetry-reduced methoxy–alkoxy derivatives and symmetrical nona-alkoxy-triphenylbenzenes, respectively. Based on X-ray diffraction data a stacking model was proposed in which the single molecules aggregate to helical columns forming a mesophase.
In particular, Scherowsky38 and Kotha24 reported that bisalkoxy-substituted 1,3,5-triphenylbenzenes do not show any mesomorphic properties. Only for the corresponding donor–acceptor complexes with trinitrofluorenone (TNF) and C8 chains in the triphenylbenzene columnar mesophases were observed. In light of these results24,38 triphenylbenzenes 5 with only six short alkoxy substituents (<C9) were deemed unsuitable as mesogens and thus only hexa- and nona-substituted derivatives bearing longer side chains (C9–C18) were considered further. We were curious whether the missing link in star shaped discotics, i.e. the simple bis- or trisalkoxy-substituted triphenylbenzenes with columnar mesomorphism in the neat form, could be obtained. In addition, due to the fact that the corresponding planar tris(trialkoxyphenyl)triazine 331 and tris(trialkoxyphenyl)boroxine 439 display stable columnar mesophases over a broad temperature range, it was of interest how the propeller-shape of triphenylbenzenes 5–7 affects the self-assembly behaviour in comparison with 3 and 4. The results are reported below.
Triphenylbenzenes 6 with decreased symmetry in the substitution pattern of the aryl ring were synthesized from commercially available 1,2,3-trimethoxy-5-bromobenzene 9 (Scheme 3). Selective demethylation of 9,41 Williamson etherification and borylation gave methoxy-bisalkoxy-substituted borolanes 11, which were submitted to Suzuki cross-coupling providing the desired triphenylbenzenes 6 in 10–25% total yield.
The symmetrically nona-alkoxy-substituted triphenylbenzenes 7 were accessible in 16–17% total yield from 9via borolane 1240 followed by Suzuki cross-coupling, demethylation and finally Williamson etherification (Scheme 3). This route is advantageous due to the less amount of expensive reagent BBr3 for the demethylation of 13 to 1438 and fewer purification steps.
Compd | Phase | T m (°C) (ΔH/kJ mol−1) | Phase | T c (°C) (ΔH/kJ mol−1) | Phase | Cycles |
---|---|---|---|---|---|---|
a Melting point (Tm), clearing point (Tc), glass transition temperature (Tg), crystalline phase (Cr), and glassy state (G). Colh: columnar hexagonal phase, Colho: ordered columnar hexagonal phase, and I: isotropic liquid. | ||||||
6a | G | 53 (Tg) | Colho | 126 (30.0) | I | 2nd heating |
G | 90 (Tg) | Colho | 123 (30.4) | I | 2nd cooling | |
6b | G | 51 (Tg) | Colho | 121 (35.4) | I | 2nd heating |
G | 86 (Tg) | Colho | 119 (34.3) | I | 2nd cooling | |
6c | Cr | 35 (33.2) | Colh | 113 (27.7) | I | 2nd heating |
Cr | 5 (20.1) | Colh | 113 (30.5) | I | 2nd cooling | |
6d | Cr | 52 (55.1) | Colh | 110 (25.3) | I | 2nd heating |
Cr | 23 (41.7) | Colh | 110 (24.5) | I | 2nd cooling | |
7a | Cr | 29 (41.3) | Colho | 143 (63.3) | I | 2nd heating |
Cr | 28 (42.5) | Colho | 139 (68.8) | I | 2nd cooling | |
7b | Cr | 41 (40.9) | Colho | 140 (67.0) | I | 2nd heating |
Cr | 38 (40.8) | Colho | 135 (69.7) | I | 2nd cooling | |
7c | Cr | 49 (74.1) | Colho | 136 (66.9) | I | 2nd heating |
Cr | 47 (52.3) | Colho | 131 (67.1) | I | 2nd cooling | |
7d | Cr | 59 (98.3) | Colho | 130 (63.1) | I | 2nd heating |
Cr | 52 (82.0) | Colho | 127 (58.9) | I | 2nd cooling |
In contrast to the sixfold substituted derivatives 5 tris(dialkoxy-methoxyphenyl)benzenes 6 displayed different phase behaviour depending on their chain lengths. For 6a,b with shorter alkyl chains (C9 and C10) no melting points were visible, neither in the heating nor in the cooling scans. Both derivatives showed distinctive glass transitions at 53 °C and 51 °C, respectively, in the second heating cycle. Upon further heating clearing from the mesophase to the isotropic liquid took place at 126 °C for 6a and 121 °C for 6b. In the cooling cycle formation of the mesophase took place at 123 °C and 119 °C, respectively. The glass transitions were shifted to higher temperatures (90 °C for 6a and 86 °C for 6b) reducing the mesophase width by half to 33 K for both compounds.
Triphenylbenzenes 6c and 6d with longer alkoxy side chains (C11 and C12) displayed reproducible melting, at 35 °C and 52 °C, and clearing peaks at 113 °C and 110 °C, respectively, upon heating. Whilst the temperatures of the clearing points are maintained in the cooling cycle with respect to those measured upon heating supercooling was observed for the mesophase-to-crystalline transitions. Crystallisation took place at 5 °C and 23 °C, respectively, giving mesophase widths of 108 K for 6c and 87 K for 6d.
All tris(trialkoxyphenyl)benzenes 7a–d formed stable mesophases, displaying increasing melting points from 29 °C (7a) to 59 °C (7d) with increasing chain lengths. Conversely, the clearing points decreased with increasing chain length from 143 °C (7a) to 130 °C (7d) whereby the mesophase widths decrease linearly through the series with increasing alkoxy chain length. This behaviour is in good agreement with the structurally related triphenylboroxine 4.39
Under a polarizing optical microscope (POM) all compounds gave textures typical of those for columnar mesophases (Fig. 1). 6a and 7a displayed broken fan textures, 6c displayed a pseudo-focal conic texture, and 6b, 6d and 7b–d displayed fan-shaped textures.42 All textures also exhibited small homeotropic areas which are common for uniaxial columnar mesophases.
Fig. 1 POM images of 6a–d and 7a–d upon cooling from the isotropic liquid (cooling rate 1 K min−1 and magnification ×100). |
Fig. 2 SAXS profile and diffraction pattern (inset) during cooling of (a) 6a at 105 °C and (b) 6d 85 °C. |
The small-angle X-ray scattering profile and the diffraction pattern of 7b are depicted in Fig. 3a. The SAXS pattern (Fig. 3a inset) is highly ordered and exhibits an oriented hexagon of the innermost reflection together with four additional sets of oriented reflections. Integration of the inner hexagon over 2Θ is shown in Fig. 3b. The relative angle of 60(±2)° between the peaks indicates a hexagonal columnar mesophase. In the small-angle region five reflections were visible in a ratio of 1:1/√3:1/2:1/√7:1/√9 which were indicated as (10), (11), (20), (21) and (30), confirming a hexagonal lattice (Fig. 3a).43
The SAXS investigations of 7d (Fig. 3c) confirmed the results of the previous XRD experiments. The SAXS profile displayed five reflections in the ratio of 1:1/√3:1/2:1/√7:1/√12 which fit to a hexagonal lattice and were therefore indicated as (10), (11), (21), (30), and (22) (Fig. 3c).
In the wide-angle region of 6d and 7b a broad halo at d = 4.5 Å and d = 4.3 Å was visible related to the liquid-like alkoxy chains (Fig. 4a and b). In addition, the wide-angle X-ray scattering profile of 7b showed a multitude of discernable reflections labelled (10), (11), (20), (21), (30), (22) and (40) besides the halo at d = 4.6 Å and a peak at d = 4.3 Å, which originate from π–π interactions between the aromatic cores and correspond to their mean distance within the columns. The latter reflection suggested the formation of an ordered columnar hexagonal mesophase.
Fig. 4 (a) WAXS profile and diffraction pattern (inset) of 6d during cooling at 85 °C and (b) WAXS profile and diffraction pattern (inset) of 7b during cooling at 88 °C. |
For compounds 6a and 7d the WAXS samples were prepared by fibre extrusion. Due to the better alignment of the sample in the WAXS of 7d as compared to 6a the former was analysed first. The WAXS pattern of 7d showed two sets of diffraction peaks, one in the equatorial and one in the meridional region (Fig. 5a on the left side). The reflexes in the equatorial region, perpendicular to the fibre axis, correspond to the lattice geometry of the mesophase which was determined as columnar hexagonal (Fig. 3c). The meridional region displayed four pairs of scattering peaks on the left and right hand side of the meridian and two distinct reflexes on the meridian axis, typical for helical superstructures. The obtained WAXS pattern is in good agreement with the simulated one shown in Fig. 5a on the right.45 For this simulation it was assumed that, because of their C3 symmetry, the molecules stack in a manner where they are rotated by φ = 60°. Thus the inner benzene rings are piled up on top of each other while the outer phenyl groups describe a triple helix around the inner column. Owing to the C3-symmetry of the triphenylbenzenes only the reflexes on the layer lines L = 3 and L = 6 are visible. The reflex on the meridional axis on the layer line L = 6 corresponds to the stacking inside of the column giving a stacking distance of d = 4.3 Å. The layer line L = 3 corresponds to the pitch p of the helix, which is three molecules or p = 8.6 Å. Altogether the WAXS pattern of 7d indicates that a triple 61 helix with an azimuthal rotation angle of φ = 60°, a pitch p = 8.6 Å and a repeat C of three pitches, giving C = 25.8 Å, is formed (Fig. 5b). Although this resembles an antiparallel “zig-zag” like packing, the high orientation in the WAXS pattern indicated a periodical setup where the peripheral phenyl rings are twisted in the same direction respective to each other. In an antiparallel stacking a random orientation would be expected.
The WAXS diffractogram of 6a (Fig. 5c on the left side) displayed a similar structure to that of 7d, although the scattering peaks on the equatorial axis were not visible. In the meridional region four peaks on the right and left hand side of the axis were visible as well as two distinct reflexes on the meridional axis. With the assumption of the same rotational angle as for 7d (φ = 60°) a diffraction pattern was simulated which is in good agreement with the measurement.45 The stacking distance inside the column at L = 6 is d = 4.0 Å which leads to slightly different helical coefficients from those for 7d.
The analysis of the WAXS pattern indicates the formation of a triple 61 helix with a rotational angle of φ = 60°, a pitch of p = 8.0 Å and a repeat of C = 24.0 Å. In both cases, indication of the handedness could not be obtained. The helix formation seems to be a statistical process due to the absence of chiral information in the triphenylbenzenes, in contrast to the recent work of Casado et al.46 who studied C3 tricarboxamides bearing chiral side chains by ECD, VPC and ECL techniques.
The X-ray data of 6a and 7d indicate a helical structure of the formed columns. In a helical setup parts of the voids resulted from the rigid star shape (Fig. 6a) can be compensated by the twisted outer phenyl rings above and beneath each disk in the column, respectively (Fig. 6b). The remaining empty spaces then have to be filled by the peripheral alkoxy chains. This can be achieved either by backfolding of the side chains or by their interdigitation.11,50 Both effects should lead to a reduced diameter of the discs (determined by the lattice spacings a of the Colh phase geometry) as can be seen in Table 2. For example, the estimated diameters for 6d and 7d are the same yet the measured matrix parameter of 6d is considerably smaller than that of 7d, indicating that the compensation of the minimalistic methoxy groups requires more backfolding or interdigitation of the remaining alkoxy chains. Taking into account that the rigid core cannot take part in these effects, the resulting reduction amounts 47% for 6d and 37% for 7d, respectively.
Compd | a calcd/Å | a obsd/Å | Δa/Å | Δdalk (%) |
---|---|---|---|---|
6a | 36.4 | 25.3 | 11.1 | 44 |
6d | 43.4 | 28.4 | 15 | 47 |
7b | 37.8 | 28.3 | 9.5 | 38 |
7d | 43.4 | 31.8 | 11.6 | 37 |
The absence of mesomorphism in the series of hexa-substituted triphenylbenzenes 5b–f is not uncommon among shape persistent hekates. For structurally related hexa- and nona-alkoxy substituted triphenylboroxines39 as well as for hexa-30 and nona-alkoxy31 substituted triphenyltriazine similar behaviour has been found. This indicates that the formation of a liquid crystalline phase in these small star shaped mesogens strongly depends on the number of alkoxy substituents and not so much on their length. Apparently nine side chains are necessary for successful nanosegregation. This might originate from two effects: the additional group at each peripheral aryl unit increases the shielding of the aromatic core, thus improving segregation of the cores and stabilising columnar mesophases. Alternatively, the additional methoxy group deplanarises the remaining alkoxy chains, forcing them to fill the void between the rings.51 Considering this, both possibilities lead to the fact that any substituent in the 5-position of the outer phenyl groups should promote mesomorphism. To elucidate this interesting topic further investigations are currently in progress.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sm02489g |
This journal is © The Royal Society of Chemistry 2016 |