Direct method to grasp molecular topology of mesogens through 13C-1H dipolar couplings.

A prime factor in determining liquid crystalline phase formation is the overall molecular shape since molecules undergo rotational motion about the long axis. Molecular topology deals with the connectivity of atomic centers in a given molecular architecture, ultimately giving rise to the gross molecular shape. 13C NMR has emerged as the most important technique in establishing the molecular topology of mesogens in the liquid crystalline phase. In this work, we demonstrate the utility of 13C-1H dipolar couplings determined from 2D separated local field NMR for finding the topology of three different mesogens in the liquid crystalline phase. The core unit of the investigated mesogens fundamentally differs, which may be categorized as rod-like, laterally substituted, and bent-core shapes. 1D and 2D 13C NMR measurements in the liquid crystalline phase revealed fascinating information. The 13C-1H dipolar couplings extracted from 2D NMR are found to be sensitive to topologically variant core units. This permitted us to establish the molecular topology just by looking at the 13C-1H dipolar couplings of the protonated carbons of the constituent phenyl rings. By considering the dipolar couplings of rod-like mesogens as a reference, the large variation in the magnitude of 13C-1H dipolar couplings of the laterally substituted and bent-core mesogens is attributed to changes in the topology of their core units. The order parameters estimated from 13C-1H dipolar couplings enabled visualization of the ordering array of phenyl rings of the mesogens. Interestingly large 13C-1H dipolar couplings are observed for mesogens in which (a) laterally located phenyl ring and (b) central phenyl ring of bent-core mesogens exhibited different trends as revealed by the orientational order parameters.

Strikingly different molecular organization and molecular order of tetracatenar mesogens in columnar mesophases revealed by XRD and 13C NMR.

For a successful design of functional mesogens, it is paramount to understand factors that contribute to molecular organisation such as molecular shape, the non-covalent interactions of the constituent moieties as well as nanosegregation of incompatible molecular parts. In this study on four tetracatenar mesogens, we show that by a slight change in the length of the terminal chain, the molecular organization changes from lamellar to columnar phase and that the orientational order experiences profound change between the lamellar, the center rectangular columnar and the hexagonal columnar mesophases. We consider here, mesogens that exhibit lamellar and columnar mesophases with five phenyl rings in the central rod-like core which are subjected to XRD and high resolution solid state 13C NMR investigations in their mesophases. The XRD studies indicate that the lower homologs exhibit a lamellar mesophase while the higher homologs show either a centre rectangular columnar phase or a 2D hexagonal columnar mesophase. 13C NMR investigations reveal interesting and strikingly different molecular orientations in each of these phases. For example, values of order parameters of one of the phenyl rings in the core region of the mesogens vary from 0.75 and 0.77 for the lamellar mesogens to 0.45 and 0.17 for the centre rectangular columnar and the hexagonal columnar mesogens respectively. While these values indicate that the mesogenic molecules are oriented along the magnetic field as expected in the lamellar phases, the very low order parameter in the hexagonal columnar phase arises due to molecules distributed azimuthally in layers and undergoing motion about the columnar axis which itself is oriented orthogonal to the magnetic field. Such cutting edge information extracted from the combined use of XRD and 13C NMR studies on tetracatenar mesogens is expected to be of significant use for the study of π-conjugated polycatenar systems where functional properties depend on the molecular orientation and order.

13 C NMR investigations of molecular order of rod-like, bent-core, and thiophene mesogens.

In this review, methods to obtain the orientational order of topologically variant molecular mesogens using by one- and two-dimensional (2D) solid-state 13 C nuclear magnetic resonance (NMR) spectroscopy are described. Besides 13 C chemical shifts, the 13 C─1 H dipolar couplings measured from 2D-separated local field (SLF) technique are used for computing the order parameters of a variety of mesogens. The investigated molecules are composed of a variable number of rings in the core, that is, core ranging from simply one ring to five rings. Among the mesogens investigated, a special focus has been placed on mesogens with thiophene rings, which are gaining popularity as liquid crystalline organic semiconductors. The replacement of a phenyl ring by thiophene in the core has a dramatic influence on molecular topology, as observed from the measured order parameters. The review highlights the advantages of the 2D SLF method for understanding the local dynamics and for mapping the topology of mesogens through the measured order parameters. SLF NMR studies of as many as 24 molecular mesogens that vary in terms of the molecular structure as well as topology are covered in the review. Order parameters of the rings have been estimated from the 13 C─1 H dipolar couplings in the nematic, smectic A, smectic C, and tilted hexatic phases as well as in B1 and B2 mesophases of various mesogens. It is anticipated that, in the years to come, the 2D SLF method would provide advanced molecular information on structurally complex mesogens that are emerging in liquid crystal science through the incessant efforts of synthetic chemists. The mini review covers the orientational order of topologically variant molecular mesogens determined by 1D and 2D solid-state 13 C NMR spectroscopy. Accordingly, rod-like, bent-core, and thiophene mesogens were subjected to 2D SLF measurements to get the order parameters from which the topology was established. The replacement of phenyl ring by thiophene and its influence on order parameters as well as on molecular topology is also discussed.

13C NMR Investigations of Hairy-Rod-Like π-Conjugated Mesogens.

Two hairy-rod π-conjugated mesogens comprising dihexylfluorene and didecyloxyterphenyl are synthesized, and their mesophase properties are examined by hot-stage optical polarizing microscope and differential scanning calorimetry techniques. Both mesogens exhibit enantiotropic nematic mesophase with broad mesophase range. A detailed 13C NMR study is carried out in solution as well as in nematic mesophase to understand changes in the orientation of the aliphatic chains. Accordingly, the unusual NMR chemical shift value of one of the methylene carbons of the hexyl chain of fluorene moiety in solution is ascribed to ring current effect changes in nematic mesophase owing to variation in the orientation of the hexyl chain. The change in conformation of lateral and alkyl chains in the nematic phase is clearly noticed compared to isotropic solution as the molecular orientation in mesophase is governed by the orientation of the long molecular axis. Furthermore, the 13C-1H dipolar couplings obtained from 2D separated local field experiments in nematic phase aided the assignments of all of the carbons of the molecules besides offering the local order. To comprehend the orientation of the fluorene unit, three order parameters are necessary whereas for the phenyl rings, two order parameters are found to be sufficient. The molecular biaxiality ( S xx - S yy) for fluorene-based mesogen is found to be higher due to the fused nature of the moiety and the presence of dihexyl chains. The orientational ordering of π-conjugated mesogens is crucial as the optoelectronic properties of them critically depend on the orientation of the constituent chromophores. The complete mapping of order parameters of fluorene, the phenyl rings and the alkyl chains showed that despite both molecules exhibiting nematic mesophase, the orientational constraints are governed by the molecular structure as well as the rigidity of the core unit, i.e., fused versus linearly connected rings.

Molecular Order and Mesophase Investigation of Thiophene-Based Forked Mesogens.

Thiophene-based rodlike molecules constructed from a three phenyl ring core and terminal dialkoxy chains recognized as forked mesogens are synthesized, and their mesophase properties as well as the molecular order are investigated. The synthesized forked mesogens would serve as model compounds for tetracatenar or biforked mesogens. On the basis of the position of the thiophene link with the rest of the core, 2-substituted and 3-substituted mesogens are realized in which the length of the terminal alkoxy chains is varied. The mesophase properties are evaluated using a hot-stage polarizing microscope and differential scanning calorimetry. For both homologues, the appearance of either nematic phase alone or in conjunction with smectic C phase is noticed depending on the length of the terminal alkoxy chains. The existence of layer ordering characteristic of the smectic C phase is confirmed for a representative mesogen using variable-temperature powder X-ray diffraction. High-resolution solid-state (13)C NMR measurements of C12 homologues of the two series reveal orientational order parameters of all rings of the core as well as terminal chains in the liquid crystalline phase. For both homologues, because of the asymmetry of ring I, the order parameter value is higher in contrast to ring II, ring III, and the thiophene ring. The chemical shifts and (13)C-(1)H dipolar couplings of OCH2 carbons of the terminal dodecyloxy chains provide contrasting conformations, reflecting the orientational constraints. Furthermore, the investigations also reveal that the mesophase range and the tendency for layer ordering are higher for 3-substituted mesogens compared to 2-substituted homologues.

(13)C NMR Studies, Molecular Order, and Mesophase Properties of Thiophene Mesogens.

Three-ring mesogens with a core comprising thiophene linked to one phenyl ring directly and to the other via flexible ester are synthesized with terminal alkoxy chains to probe the mesophase properties and find the molecular order. The phenyl thiophene link in the core offers a comparison of the mesophase features with the molecular shape of the mesogen. The synthesized mesogens display enantiotropic polymesomorphism and accordingly nematic, smectic A, smectic C and smectic B mesophases are perceived depending upon the terminal chain length. For some of the homologues, monotropic higher order smectic phases such as smectic F and crystal E are also witnessed. The existence of polymesomorphism are originally observed by HOPM and DSC and further confirmed by powder X-ray diffraction studies. For the C8 homologue, high resolution solid state (13)C NMR spectroscopy is employed to find the molecular structure in the liquid crystalline phase and using the 2D SLF technique, the (13)C-(1)H dipolar couplings are extracted to calculate the order parameter. By comparing the ratio of local order of thiophene as well as phenyl rings, we establish the bent-core shape of the mesogen. Importantly, for assigning the carbon chemical shifts of the core unit of aligned C8 mesogen, the (13)C NMR measured in mesophase of the synthetic intermediate is employed. Thus, the proposed approach addresses the key step in the spectral assignment of target mesogens with the use of (13)C NMR data of mesomorphic intermediate.

Monolayer to interdigitated partial bilayer smectic C transition in thiophene-based spacer mesogens: X-ray diffraction and (13)C nuclear magnetic resonance studies.

Mesophase organization of molecules built with thiophene at the center and linked via flexible spacers to rigid side arm core units and terminal alkoxy chains has been investigated. Thirty homologues realized by varying the span of the spacers as well as the length of the terminal chains have been studied. In addition to the enantiotropic nematic phase observed for all the mesogens, the increase of the spacer as well as the terminal chain lengths resulted in the smectic C phase. The molecular organization in the smectic phase as investigated by temperature dependent X-ray diffraction measurements revealed an interesting behavior that depended on the length of the spacer vis-a-vis the length of the terminal chain. Thus, a tilted interdigitated partial bilayer organization was observed for molecules with a shorter spacer length, while a tilted monolayer arrangement was observed for those with a longer spacer length. High-resolution solid state (13)C NMR studies carried out for representative mesogens indicated a U-shape for all the molecules, indicating that intermolecular interactions and molecular dynamics rather than molecular shape are responsible for the observed behavior. Models for the mesophase organization have been considered and the results understood in terms of segregation of incompatible parts of the mesogens combined with steric frustration leading to the observed lamellar order.

2-Octyl thiophene based three ring mesogens: solid state (13)C NMR and XRD investigations.

2-Octyl thiophene based three-ring mesogens namely 4-n-alkoxyphenyl 4-(5-n-octyl-2-thienyl)benzoates are synthesized by employing palladium acetate based direct arylation. The alkoxy terminal is varied with even carbons from C2 to C14 and enantiotropic polymesomorphism is noticed for all the homologs. Accordingly, phase sequence consisting of nematic, smectic A, smectic C and smectic B is seen for mesogens with terminal chains C6, C8, C10 and C12 on cooling the isotropic phase. For mesogens with C2, C4, C8 and C10 terminal alkoxy chains, the mesophase assignment from hot-stage optical microscopy and differential scanning calorimetry is further confirmed by variable temperature powder X-ray diffraction measurements. The appearance of smectic B phase is established by noticing sharp and intense peaks in both small-angle and wide-angle regions. For a representative mesogen, i.e. T10, high-resolution solid-state (13)C NMR investigations are carried out in all the phases, viz. nematic, smectic A, smectic C and smectic B phases. The orientational order parameters calculated from (13)C-(1)H dipolar couplings from 2D SAMPI-4 experiments are found to be 0.44, 0.67, 0.73 and 0.79 in nematic, smectic A, smectic C and smectic B mesophases for the center phenyl ring respectively. Remarkably, the thiophene order parameter in all mesophases is found to be higher than that of phenyl rings and is explained by considering the molecular shape, which has a terminal bend. Further, the mesogens are found to be photoemissive in chloroform solution with an emission band at ∼410 nm.

Structural investigation of resorcinol based symmetrical banana mesogens by XRD, NMR and polarization measurements.

Synthesis and structural characterization of two novel symmetrical banana mesogens built from resorcinol with seven phenyl rings linked by ester and imine with a terminal dodecyl/dodecyloxy chain has been carried out. Density functional theory (DFT) has been employed for obtaining the geometry optimized structures, the dipole moments and (13)C NMR chemical shifts. The HOPM and DSC studies revealed enantiotropic B2 and B7 phases for the dodecyl and dodecyloxy homologs respectively. The powder X-ray studies of both the mesogens indicate the presence of layer ordering. The polarization measurements reveal an anti-ferroelectric switching for the B2 phase of the dodecyl homolog whose structure has been identified as SmCSPA. The B7 phase of the dodecyloxy homolog was found to be non-switchable. High resolution (13)C NMR study of the dodecyl homolog in its mesophase has been carried out. (13)C-(1)H dipolar couplings obtained from the 2-dimensional separated local field spectroscopy experiment were used to obtain the orientational order parameters of the different segments of the mesogen. Very large (13)C-(1)H dipolar couplings observed for the carbons of the central phenyl ring (9.7-12.3 kHz) in comparison to the dipolar couplings of those of the side arm phenyl rings (less than 3 kHz) are a direct consequence of the ordering in the banana phase and the shape of the molecule. From the ratio of the local order parameter values, the bent-angle of the mesogen could be determined in a straight forward manner to be 120.5°.

(13)C NMR investigations and the molecular order of 4-(trans-4'-hexylcyclohexyl)-isothiocyanatobenzene (6CHBT).

The static 1D (13)C and 2D Proton Encoded Local Field (PELF) NMR experiments are carried out in the nematic phase of a less viscous liquid crystal 4-(trans-4'-hexylcyclohexyl)-isothiocyanatobenzene (6CHBT) with a view to find orientational order. The PELF spectra provide better resolution which facilitates the assignment of cyclohexyl and phenyl ring carbons relatively easy. For the cyclohexyl unit, four pairs of dipolar splitting are clearly noticed in contrast to earlier reports on structurally similar mesogens where only two pairs of doublets are seen. The linear relationship between anisotropic chemical shifts and orientational order is established and semi-empirical parameters are obtained to aid the study of the order behaviour of 6CHBT over the entire nematic range. The data further fitted to the Haller equation and a reasonably good agreement is observed. The temperature dependence trends of orientational order parameters extracted for various carbons using (13)C-(1)H dipolar couplings with those of (13)C chemical shifts are compared. A gradual decrease in the order parameter is noticed for different molecular segments while traversing from the core to the aliphatic chain via the cyclohexyl ring. The notable decreasing trends of order parameters along the chain are observed similar to those of the corresponding phenyl cyclohexanes reported earlier.

Structural characterization and molecular order of rodlike mesogens with three- and four-ring core by XRD and 13C NMR spectroscopy.

Structural characterizations using XRD and (13)C NMR spectroscopy of two rodlike mesogens consisting of (i) three phenyl ring core with a polar cyano terminal and (ii) four phenyl ring core with flexible dodecyl terminal chain are presented. The three-ring-core mesogen with cyano terminal exhibits enantiotropic smectic A phase while the four-ring mesogen reveals polymesomorphism and shows enantiotropic nematic, smectic C, and tilted hexatic phases. The molecular organization in the three-ring mesogen is found to be partial bilayer smectic Ad type, and the interdigitation of the molecules in the neighboring layers is attributed to the presence of the polar terminal group. For the four-ring mesogen, the XRD results confirm the existence of the smectic C and the tilted hexatic mesophases. A thermal variation of the layer spacing across the smectic C phase followed by a discrete jump at the transition to the tilted hexatic phase is also observed. The tilt angles have been estimated to be about 45° in the smectic C phase and about 40° in tilted hexatic phase. (13)C NMR results indicate that in the mesophase the molecules are aligned parallel to the magnetic field. From the (13)C-(1)H dipolar couplings determined from the 2D experiments, the overall order parameter for the three-ring mesogen in its smectic A phase has been estimated to be 0.72 while values ranging from 0.88 to 0.44 have been obtained for the four-ring mesogen as it passes from the tilted hexatic to the nematic phase. The orientations of the different rings of the core unit with respect to each other and also with respect to the long axis of the molecule have also been obtained.

Determination of 13C chemical shift anisotropy tensors and molecular order of 4-hexyloxybenzoic acid.

4-Alkoxy benzoic acids belong to an important class of thermotropic liquid crystals that are structurally simple and often used as starting materials for many novel mesogens. 4-Hexyloxybenzoic acid (HBA) is a homologue of the same series and exhibits an enantiotropic nematic phase. As this molecule could serve as an ideal model compound, high resolution (13)C NMR studies of HBA in solution, solid, and liquid crystalline phases have been undertaken. In the solid state, two-dimensional separation of undistorted powder patterns by effortless recoupling (2D SUPER) experiments have been carried out to estimate the magnitude of the components of the chemical shift anisotropy (CSA) tensor of all the aromatic carbons. These values have been used subsequently for calculating the orientational order parameters in the liquid crystalline phase. The CSA values computed by density functional theory (DFT) calculations showed good agreement with the 2D SUPER values. Additionally, (13)C-(1)H dipolar couplings in the nematic phase have been determined by separated local field (SLF) spectroscopy at various temperatures and were used for computing the order parameters, which compared well with those calculated by using the chemical shifts. It is anticipated that the CSA values determined for HBA would be useful for the assignment of carbon chemical shifts and for the study of order and dynamics of structurally similar novel mesogens in their nematic phases.

Phase characterization and study of molecular order of a three-ring mesogen by 13C NMR in smectic C and nematic phases.

Molecules exhibiting a thermotropic liquid-crystalline property have acquired significant importance due to their sensitivity to external stimuli such as temperature, mechanical forces, and electric and magnetic fields. As a result, several novel mesogens have been synthesized by the introduction of various functional groups in the vicinity of the aromatic core as well as in the side chains and their properties have been studied. In the present study, we report three-ring mesogens with hydroxyl groups at one terminal. These mesogens were synthesized by a multistep route, and structural characterization was accomplished by spectral techniques. The mesophase properties were studied by hot-stage optical polarizing microscopy, differential scanning calorimetry, and small-angle X-ray scattering. An enantiotropic nematic phase was noticed for lower homologues, while an additional smectic C phase was found for higher homologues. Solid-state high-resolution natural abundance (13)C NMR studies of a typical mesogen in the solid phase and in the mesophases have been carried out. The (13)C NMR spectrum of the mesogen in the smectic C and nematic phases indicated spontaneous alignment of the molecule in the magnetic field. By utilizing the two-dimensional separated local field (SLF) NMR experiment known as SAMPI4, (13)C-(1)H dipolar couplings have been obtained, which were utilized to determine the orientational order parameters of the mesogen.

(NE,NE)-N,N-Bis(4-hex-yloxy-3-methoxy-benzyl-idene)ethane-1,2-diamine.

The title compound, C(30)H(44)N(2)O(4), was obtained from the dimerization of 4-hexyl-oxyvanillin with ethyl-enediamine in 95% methanol solution. It adopts a trans configuration with respect to the C=N bond and possesses a crystallographically imposed centre of symmetry.

Solid-state NMR characterization and determination of the orientational order of a nematogen.

Thermotropic liquid crystalline compounds are of considerable importance due to their potential applications as advanced functional materials. A mesogen consisting of a terminal dimethylamino group, which can act as a charge-transfer donor, is particularly valuable for its light emission and nonlinear optical properties. In this study, we report the solid-state NMR investigation of the nematic behavior of one such novel mesogen (4-(dodecyloxy)benzoic acid 4-[((4-(dimethylamino)phenyl)imino)methyl]phenyl ester). Static and MAS experiments were performed on nematic and crystalline phases of the compound to measure (13)C chemical shift, (13)C-(1)H dipolar coupling, and (1)H chemical shift values. 2D chemical shift correlation of (1)H and (13)C nuclei confirmed the (13)C chemical shift values determined from 1D CPMAS experiments. The appearance of more peaks in both CPMAS and (13)C-(1)H HETCOR spectra of a crystalline solid suggests the heterogeneous orientations of phenyl rings of the mesogenic core. Variable-temperature experiments infer the motional averaging of these orientations before melting. The (1)H-(13)C dipolar coupling values, measured by 2D PITANSEMA experiments, were used to determine the orientational order of the mesogenic core at various temperatures. The influence of the linking unit and terminal substituents on the order parameter values of the mesogenic core is discussed.