Helical Columns Research Articles

Hierarchical Self-Organization and Disorganization of Helical Supramolecular Columns Mediated by H-Bonding and Shape Complementarity.

H-bonding, shape complementarity, and quasi-equivalence are widely accepted as some of the most influential molecular recognition events mediating biological and synthetic self-organizations. H-bonds are weaker than ionic but stronger than van der Waals forces. However, the directionality of H-bonds makes them the most powerful among all nonbonding interactions. Here, we selected two taper-shaped self-assembling dendrons, one flexible and one rigid, and equipped them with -CO2CH3, -CH2OH, and -COOH at their apex. They demonstrated the hierarchical way in which shape-complementarity in the presence of -CO2CH3 mediated highly ordered helical self-organization for the case of the rigid building block and less ordered helical arrays for the flexible one. Weak H-bonding by -CH2OH unwound the helix from the rigid dendron, yielding a porous column. Due to its quasi-equivalence, the flexible dendron tolerated better the H-bonding by -CH2OH self-organizing a different helical column. The rigid and the flexible dendrons yielded only disorganized nonhelical columns in the presence of -COOH at the apex. This balance between rigidity, flexibility, and tolerance or lack of it to diverse H-bonding architectures indicates that mechanistic elucidation of the self-organization process helps endow it with the same building block, both helical organizations approaching biological precision, and disorganized nonhelical arrangements.

Thermotropic “Plumber's Nightmare”—A Tight Liquid Organic Double Framework

AbstractGyroid, double diamond and the body‐centred “Plumber's nightmare” are the three most common bicontinuous cubic phases in lyotropic liquid crystals and block copolymers. While the first two are also present in solvent‐free thermotropics, the latter had never been found. Containing six‐fold junctions, it was unlikely to form in the more common phases with rod‐like cores normal to the network columns, where a maximum of four branches can join at a junction. The solution has therefore been sought in side‐branched mesogens that lie in axial bundles joined at their ends by flexible “hinges”. But for the tightly packed double framework, geometric models predicted that the side‐chains should be very short. The true Plumber's nightmare reported here, using fluorescent dithienofluorenone rod‐like mesogen, has been achieved with, indeed, no side chains at all, but with 6 flexible end‐chains. Such molecules normally form columnar phases, but the key to converting a complex helical column–forming mesogen into a framework‐forming one was the addition of just one methyl group to each pendant chain. A geometry‐based explanation is given.

Chirality and odd mechanics in active columnar phases.

Chiral active materials display odd dynamical effects in both their elastic and viscous responses. We show that the most symmetric mesophase with 2D odd elasticity in three dimensions is chiral, polar, and columnar, with 2D translational order in the plane perpendicular to the columns and no elastic restoring force for their relative sliding. We derive its hydrodynamic equations from those of a chiral active variant of model H. The most striking prediction of the odd dynamics is two distinct types of column oscillation whose frequencies do not vanish at zero wavenumber. In addition, activity leads to a buckling instability coming from the generic force-dipole active stress analogous to the mechanical Helfrich-Hurault instability in passive materials, while the chiral torque-dipole active stress fundamentally modifies the instability by the selection of helical column undulations.

Designing Highly Ordered Helical and Nonhelical Porous Crystalline and Disordered Nonhelical Columnar Liquid Crystalline Self-Organizations.

Helical self-organizations are equilibrium structures responsible for the assembly of nonequilibrium and equilibrium living and synthetic systems. Racemic helical columnar systems transform into one-handed systems with the help of enantiomerically rich or pure components. Racemic, enantiomerically rich, and enantiomerically pure helical periodic arrays of columns are analyzed by oriented fiber X-ray diffraction (XRD). With few exceptions, highly ordered helical 3-D organizations as generated from homochiral columns cannot be obtained from achiral, racemic, or enantiomerically rich helical columns. Here, we report an unprecedented class of nonhelical porous ordered, disordered nonhelical columnar liquid crystalline (LC) self-organizations and columnar liquids constructed from AB4 to AB9 isomeric terphenyls by molecular design unwinding of a 3-D helical organization. A library of 16 nonhelical porous ordered, disordered columnar and four liquids was designed by employing as a model a closely related achiral AB4 meta-terphenyl, which self-organizes one of the most perfect synthetic ordered columnar hexagonal helices known. A general molecular mechanism to unwind highly ordered 3-D helices into nonhelical porous columnar ordered LCs and liquids was elaborated to design this transformation, which provided unprecedented nonequilibrium synthetic systems. This methodology is expected to be general for transformation of helical macromolecular and supramolecular organizations into nonhelical crystals, LCs, and liquids.

Multicomponent mass transfer modeling of antagonistic binary adsorption of metallic pollutants from water using helical fixed-bed columns

A multicomponent advection-dispersion model was proposed to simulate the breakthrough curves of antagonistic adsorption of zinc, nickel and cadmium cations from water using helical fixed-bed columns packed with bone char. It was formulated using a linear driving force model, empirical multicomponent Langmuir-based isotherm and retardation coefficient to correlate the experimental breakthrough curves obtained for different binary (metal 1 + metal 2) aqueous solutions, which showed a higher asymmetry degree because of the antagonistic adsorption and axial dispersion impact in this complex fixed-bed configuration. Several parameters of this model were handled as column feed concentration dependent to improve the results of data fitting. The experimental results indicated the presence of a strong antagonistic adsorption effect of zinc and cadmium cations, causing the nickel breakthrough curves to show a clear desorption process (i.e., a displacement effect of the ions already adsorbed on the bone char surface commonly known as roll up) during helical column operation. Experimental bed adsorption capacities ranged from 0.03 to 0.74 mmol/g. The proposed advection-dispersion model fitted the experimental breakthrough profiles satisfactorily for the tested binary adsorption systems, including the desorption zone where the mean modeling errors were lower than 10 % for tested mixtures. Several column operation and mass transfer parameters were calculated and discussed to analyze the separation performance of the tested helical fixed-bed bone char columns. These results suggest that the proposed advection-dispersion model can simulate the multicomponent antagonistic adsorption of relevant water pollutants using intensified adsorption equipment such as helical fixed-bed columns.

Przykłady Małej Architektury w oparciu o System Arm-Z

Arm-Z is a conceptual hyperredundant robotic manipulator composed on linearly joined number of identical modules. Each of them has one-degree-of-freedom (1-DOF) – the relative twist. Since modules are congruent, Arm-Z presents potential economical advantages and enhanced robustness. The modules can be mass produced and easily replaceable. The control of Arm-Z, however, is difficult and not intuitive. Therefore it most often requires the use of computational intelligence techniques. This article presents selected concepts for kinetic street furniture based on Arm-Z: a helical column of adjustable height, a sun tracking shade or solar energy harvesting device, bio-mimicing sculpture, sprinkler or fountain. All these ideas are based on low-tech approach. For this purpose, the initial unit in the chain is fixed to the solid foundation. For simplicity, the drive is applied directly to the first unit and transferred by the means of internal gears to the following modules. All of them are equipped with a set of cylindrical and bevel gears with straight teeth with involute profile (for connecting the modules).

Self-Assembly Behavior, Aggregation Structure, and the Charge Carrier Transport Properties of S-Heterocyclic Annulated Perylene Diimide Derivatives.

The construction of high-performance n-type semiconductors is crucial for the advancement of organic electronics. As an attractive n-type semiconductor, molecular systems based on perylene diimide derivatives (PDIs) have been extensively investigated over recent years. Owing to the fascinating aggregated structure and high performance, S-heterocyclic annulated PDIs (SPDIs) are receiving increasing attention. However, the relationship between the structure and the electrical properties of SPDIs has not been deeply revealed, restricting the progress of PDI-based organic electronics. Here, we developed two novel SPDIs with linear and dendronized substituents in the imide position, named linear SPDI and dendronized SPDI, respectively. A series of structural and property characterizations indicated that linear SPDI formed a long-range-ordered crystalline structure based on helical supramolecular columns, while dendronized SPDI, with longer alkyl side chains, formed a 3D-ordered crystalline structure at a low temperature, which transformed into a hexagonal columnar liquid crystal structure at a high temperature. Moreover, no significant charge carrier transport signal was examined for linear SPDI, while dendronized SPDI had a charge carrier mobility of 3.5 × 10-3 cm2 V-1 s-1 and 2.1 × 10-3 cm2 V-1 s-1 in the crystalline and liquid crystalline state, respectively. These findings highlight the importance of the structure-function relationship in PDIs, and also offer useful roadmaps for the design of high-performance organic electronics for down-to-earth applications.

Behavior of helical reinforced concrete columns subjected to cyclic loading

AbstractHelical concrete columns are a new type of structural members which arose in new twisted buildings to satisfy architectural purposes. Helical concrete columns have a unique geometry which depends on the values of twist angle (ϕ) and the tilt distance of the center of rotation. According to the ACI T1.1R-01:2001 guidelines, a combined effect of axial load and lateral cyclic displacement protocol was applied to twelve specimens. Nonlinear finite element method was used to conduct the analysis and the numerical simulation for the helical reinforced concrete columns. The findings of the study revealed that the value of the buckling load, lateral displacement and the drift angle of helical concrete columns are significantly affected by the tilting distance of the rotation center and the twist angle.

Porous helical supramolecular columns self-organized via the fluorophobic effect of a semifluorinated tapered dendron.

The self-organizable dendron (4-3,4-3,5)12G2X with X = -CO2CH3 and -CH2OH, an already classic dendron, facilitating the formation of a large diversity of columnar hexagonal phases including crystalline, with intracolumnar order, and liquid crystalline, and providing access for the first time to mimics of the transmembrane protein water channel Aquaporin was semifluorinated at eight of the sp3 hybridized carbons of its alkyl groups to provide (4-3,4-3,5)4F8G2X. The self-organization of (4-3,4-3,5)4F8G2X was analyzed by a combination of oriented fiber intermediate angle X-ray scattering, wide angle X-ray scattering, electron density maps, and reconstructed X-ray diffractograms by emplying molecular models. These experiments demonstrated that fluorophobic effect of (4-3,4-3,5)4F8G2X mediated mostly via the helical confiormation of the fluorinated fragments sharper miocrosegregation of the fluorinated fragments in the most ordered states of the resulting 124 helical porous columns. These results support the original model of self-organization of dendrons and provide access to new and simpler synthetic avenues for the construction of mimics of aquaporin channels which are of great interest for cell biology and for the next generation of membranes for water separation and water purification.

Axial Compression Behavior of Large-Diameter, Concrete-Filled, Thin-Walled Galvanized Helical Corrugated Steel Tubes Column Embedded with Rebar

Thin-walled galvanized helical corrugated steel tubes (HCSTs) filled with concrete are promising composite members, consisting of concrete, an anti-corrosion shell, and a multifunctional exterior corrugated steel tube. To investigate the synergistic working mechanism of concrete-filled HCSTs (CFHCSTs), six specimens were designed for axial compression tests, with the inner diameter of the column and the volumetric steel ratios of the longitudinal reinforcement as the variation parameters. The results show that HCSTs can better confine the concrete core and increase its strength. The failure mode of HCSTs is significantly influenced by the column’s diameter, and those with a smaller diameter are prone to slide failure and lock seam tearing. The strains and stresses on HCSTs are discussed in detail to elucidate the confinement effect. This paper proposes a suitable design method to predict the ultimate axial compression load capacity of CFHCST columns based on early studies on steel tube-confined concrete.

Bridging organic, molecular, macromolecular, supramolecular and biological sciences to create functions via fluorine chemistry and fluorinated reagents

After a brief introduction highlighting the challenges of fluorine chemistry and the latest developments in the field, this Perspective will discuss how a combination of fluorine and fluorous chemistry together with fluorinated reagents helped to bridge between organic, molecular, macromolecular, supramolecular and biological sciences to create functions in the laboratory of the corresponding author. The reactivity of fluoride as a leaving group is best illustrated by SNAr reactions when it helped to demonstrate single electron transfer-mediated side reactions and through molecular design replaced activated aryl fluorides with aryl chlorides in the synthesis of poly(etherketone)s. Subsequently it was demonstrated how Ni(II) sigma complexes provided an orthogonal approach to the Suzuki-type cross-coupling of arylfluorides, other halides and all aryl C–O based electrophiles. Fluorinated reagents facilitated cylotrimetrization vs cyclotetramerization of bis(methoxy)benzyl chloride and alcohol and the synthesis of the simplest molecular liquid crystals. Triflic acid, methyl triflate facilitated the most tolerant living polymerizations including of cyclic siloxanes, functional vinyl ethers and oxazolines to generate self-organizable dendronized polymers while fluorine, trifluoromethyl and trifluoromethoxy groups facilitated disassembly and reassembly of liquid crystal polyethers and poly(p-phenylenes). Fluorinated stereocenters accessed the first heterochiral recognition in side-chain liquid crystal poly(vinyl ether)s and their model compounds. Alkali metal triflates mediated self-organization of supramolecular nonfluorinated and fluorinated self-assembling minidendrons, dendrons, dendrimers and self-organizable dendronized polymers. The role of fluorinated alkyl groups and of alkali metal triflates in the self-assembly, disassembly and isomorphic replacement analysis, of supramolecular helical columns, of the assembly of helical cogwheel coat and of spherical supramolecular dendrimers forming Frank-Kasper periodic and quasiperiodic arrays was highlighted. A brief discussion of fluorinated amino acids, peptides and peptoids and their potential role in the self-assembly and functions resulted from dendritic dipeptides followed by a discussion of semifluorinated amphiphilic Janus dendrimers as models of biological membranes, including for cell fusion and fission, concludes this Perspective.

Molecular design principles of helical pyramidal chirality self-organized from achiral hexakis(alkyloxy)triphenylene

2,3,6,7,10,11-Hexakis(alkyloxy)triphenylene (HATn) containing n = 4 to 12 carbons in its alkyl groups, are a classic group of discotic molecules self-organizing columnar liquid crystals. The structure of the crystalline assemblies of these discotic molecules were neglected since they were invented 45 years ago. Recently, we discovered that the crystal state of HAT4 consists of a highly ordered 8/1 helical chiral pyramidal 3D self-organization. In this publication we report the structural analysis of all 3D self-organizations of HATn containing n = 4 to 12 carbons in their achiral alkyls. Unexpectedly, the highly ordered 8/1 helical chiral pyramidal crystalline columns assembled from the crown-conformation of HAT4 is encountered also in the crystalline periodic array of HAT5. HAT6 self-organizes a 5/1 helical chiral pyramidal 3D column. HAT7 to HAT10 maintain their crown conformation in their 3D supramolecular pyramidal columns. However, their 3D pyramidal assemblies exhibit a nonhelical criss-cross arrangement. HAT11 and HAT12 self-organize 3D nonhelical columns from criss-cross arrangements of disc-like conformers. The structures of all these 3D helical and nonhelical pyramidal as well as of nonhelical discotic columns were resolved for the first time at the molecular level by reconstruction of their oriented fiber X-ray diffractograms with the help of molecular models. These results demonstrate that a single self-assembling building block can self-organize either helical chiral pyramidal or nonhelical pyramidal or even nonhelical discotic assemblies via two of its constitutional isomers. This outcome prompts essential questions related to the current standing of helical self-organizations. The most important question is, why over the past many years the scientific community explored helical self-organizations derived from long alkyl groups when the ideal alkyls for this process seem to be short? A hypothetic explanation of the findings reported here and of their impact on the field of helical self-organizations is presented.

A chiral SrSi2 (srs) superstructure constructed by a dual interaction system showing isotropic electrical conductivity

Most porous conductive frameworks are highly anisotropic in their structures thus leading to anisotropic charge transport. Here we report a supramolecular self-assembly which is constructed by intermolecular hydrogen bonding and π···π interactions. This material features a chiral, porous, cubic framework structure with π-stacked helical columns along all of the three Cartesian coordinates. As a result, isotropic charge transport with an electrical conductivity (σ) of 2.1 × 10–7 S/cm is achieved. By achieving isotropic charge transport in a π-stacked supramolecular assembly, these results provide a new type of isotropic conductive framework materials alternative to conductive metal-organic frameworks (MOFs).

A highly ordered 8/1 helical pyramidal column self-organized from the crown conformation of achiral hexa(butyloxy)triphenylene

Liquid crystals of disc-like molecules are known for 45 years. 2,3,6,7,10,11-Hexakis(alkyloxy)triphenylene (HATn) containing n = 4 to 11 carbons in its achiral alkyl groups, represents one of the classic families of disc-like molecules. X-ray analysis suggested that disc-like molecules stack on top of each other at irregular spacing in columns distributed in the melt of their alkyl groups forming discotic or columnar or discotic nematic liquid crystals. Interest in discotic liquid crystals comes mostly from their conducting and photoconducting properties. While writing a recent perspective on the 45th anniversary of discotic liquid crystals we realized that the molecular structures of the 3D crystal and 2D liquid crystal phases of discotic molecules were never determined at the molecular level, in spite of the great interest in their physical properties. Since structure determines function, we decided to perform a detailed investigation of the molecular structure of HATn self-organizations by reconstructing their oriented fiber X-ray diffractograms both in the crystal and liquid crystal states. This communication reports the synthesis, analysis by differential scanning calorimetry of HATn containing n = 4 to 12 carbons in its achiral alkyl groups and the molecular structure of HAT4 in its crystal and liquid crystal states. Unexpectedly, a highly ordered 8/1 helical pyramidal crystalline column assembled from a crown-like conformation of the HAT4 and a non-helical column of the discotic liquid crystal state, the last similar to the original suggested supramolecular structure, were resolved for the first time at the molecular level. These preliminary results raise a lot of fundamental issues in the area of discotic and columnar self-organizations and of related helical columnar self-organizations generated with different building blocks and belonging to different disciplines. A comprehensive mechanistic elucidation of the molecular details of helical and non-helical self-organizations in synthetic complex systems may become as influential in the field of soft condensed matter as that of helical and non-helical self-organizations in the field of molecular biology.

Discotic liquid crystals 45 years later. Dendronized discs and crowns increase liquid crystal complexity to columnar from spheres, cubic Frank-Kasper, liquid quasicrystals and memory-effect induced columnar-bundles

In 1977 Chandrasekhar laboratory reported the first examples of a new class of thermotropic liquid crystals self-organized from planar disc-like molecules substituted with alkyl groups. X-ray analysis demonstrated that these disc-like molecules stack on top of each other at irregular spacing in columns located in the paraffin melt of their alkyl groups. These supramolecular columns self-organize in a hexagonal array defined as the new thermotropic discotic or columnar hexagonal liquid crystal phase. This new thermotropic liquid crystal phase has translational periodicity in two dimensions and liquid-like disorder in the third one, along the column axis. In 2002 Bushby and Lozman dedicated a brief review article to the 25 anniversary of discotic liquid crystals. This review also included a brief discussion of supramolecular discs and columns self-organized from self-assembling dendrons and dendrimers. The current publication is not another review but a brief perspective on new liquid crystal phases self-organized from dendronized rigid planar and conformationally flexible discs as well as from crown-like molecules. Crown-like molecules are the most stable conformation of a transient unstable disc. All dendronized disc-like and crown molecules adopt a crown conformation that self-assemble helical columns and spherical helices. A large diversity of new liquid crystalline phases self-organize from these helical columns and spherical helices. They include helical columnar hexagonal phases from crowns and from supramolecular spheres, Frank-Kasper A15 (known as cubic phase of space group Pm3¯n), σ phase (also known as tetragonal of space group P42/mnm), 12-fold quasi liquid crystals (QLC) and supramolecular orientational memory (SOM) derived complex bundles of supramolecular columnar hexagonal arrays that are not yet completely elucidated. The impact of Chandrasekhar on the discovery of self-assembling dendrons and dendrimers via his biaxial nematic liquid crystal concept will also be discussed. This perspective is dedicated to the 45 anniversary of the discovery of discotic liquid crystals and to the memory of Professor Sivaramakrishna Chandrasekhar, a modest, respectful and great scientist.

Searching for the simplest self-assembling dendron to study helical self-organization and supramolecular polymerization

The first generation self-assembling dendron (4Bp-3,4)nG1CO2CH3 where Bp is biphenyl, n is an achiral linear, n-dodecyl, or branched chiral alkyl group, (S)-3,7-dimethyl-octyl (dm8*) undergoes helical self-organization in bulk state and in solution. The supramolecular columns assembled from this dendron are helical, regardless, if the alkyl groups on its periphery are achiral or chiral. This demonstrates self-organization of helical columns both from achiral and chiral dendrons and reveals that the role of the stereocenter is to select the helical sense of an already helical column. This very simple self-assembling dendron can be subjected to a large diversity of chemical modifications and functionalization, all expecting to maintain the helical function in bulk and in solution in the range of temperature of interest to investigate helical self-organization and supramolecular polymerization.

Helical Packing Columns for Preventing Foam Formation: Experimental and Numerical Investigations

AbstractUnwanted foaming and liquid bridging inside structured packings have a negative effect on the pressure drop during thermal separation processes. A novel helical design of a packing column for preventing foaming is presented. The effective interfacial area is calculated by numerical simulations. Different designs are analyzed by varying geometrical parameters such as helix pitch, channel opening angle, and number of channels. Different F‐factor values and liquid loads are evaluated. Packings with larger helix pitch exhibited lower pressure drop and reduced effective interfacial area. Smaller channel opening angles increased the pressure drop and promoted unstable flow conditions. The novel packings show lower effective interfacial area than existing structured packings, but no foaming was observed in a wide range of operating conditions.

1,4]Ditellurino[2,3-b:5,6-b']di-pyrazine.

[1,4]Ditellurino[2,3-b:5,6-b']di-pyrazine represents the first reported [1,4]chalcogena[2,3-b:5,6-b']di-pyrazine containing a heavy chalcogens The asymmetric unit consists of three mol-ecules. In contrast to its sulfur analog, which is planar [Lynch et al. (1994 ▸) Cryst. Struct. Commun. 50,1470-1472], C8H4N4Te2 is folded along the Te⋯Te axis to accommodate the larger chalcogenide atoms. The dihedral angle between the two Te2C2 rings of the central ring is 57.9° (mean of three). C-Te bond lengths range from 2.1105 (16) Å to 2.1381 (17) Å, in good agreement with those predicted by their covalent radii. All Te atoms are involved in inter-molecular Te⋯N contacts, with distances in the range 2.894 (2) to 2.963 (2) Å. These result in a spiral supra-molecular assembly, forming helical columns.

Molecular parameters including fluorination program order during hierarchical helical self-organization of self-assembling dendrons

Primary structure endows tertiary structure while tertiary structure determines function. This fundamental principle is responsible for the generation of high order and precise functions in both biological assemblies including giant and mega proteins and nucleic acids as well as in metals generated from only few atoms. However, this size-independent ability to generate high order and very precise functions is not yet accessible in non-biological assemblies that use the same principles for their hierarchical self-organization. Here we report a study investigating the role of the molecular parameters on the hierarchical self-organizations of helical columnar assemblies produced from the column-forming self-assembling dendron (4-3,4-3,5)-X with a linear or branched hydrogenated or linear semifluorinated alkyl groups while apex is -CO2CH3 or -CH2OH. A combination of differential scanning calorimetry, small and wide-angle powder and oriented fiber X-ray diffraction experiments together with helical diffraction theory, 2-D and 3-D electron density maps were employed in these structural analysis experiments. They demonstrated that H-bonding at the apex of the self-assembling dendron enhanced the order of the helical columns by comparison with the order of supramolecular helical columns based on dendrons containing an ester group at their apex. This was the case for both linear and branched alkyl groups at the periphery of the self-assembling dendron. Unexpectedly, self-assembling dendrons containing semifluorinated alkyl groups on their periphery and H-bonding groups at their apex increase even more the order of their supramolecular perfluorinated porous helical column. In all cases helix is mediated by the aromatic part of the dendron but hierarchically influenced both by the apex and peripheral groups. A combination of branched alkyl groups with H-bonding at the apex produced a new mechanism to transform helical columns assembled from the column-forming (4-3,4-3,5)-X self-assembling dendron into spherical assemblies, organized from conical dendron conformers, forming an A15 Frank-Kasper phase.

Enhancing conformational flexibility of dendronized triphenylene via diethylene glycol linkers lowers transitions of helical columnar, Frank-Kasper, and quasicrystal phases

A library of triphenylene (Tp) dendronized with self-assembling dendrons via a diethylene glycol linker was synthesized and the corresponding self-organizations were analyzed. They self-organize via a crown conformation in helical columns and spherical helices that produce hexagonal columnar, Frank-Kasper and soft quasicrystal assemblies. The same self-organizations are produced in the absence of the diethylene glycol linker except that the phase transitions and isotropization temperatures occur at lower temperatures in the presence of the linker. The incorporation of the flexible diethylene glycol linker induces also strong π-π stacking in helical columns. Spherical helices are spherical distorted short fragments of helical columns and therefore the same principles determine the thermal stability of the hexagonal columnar and of Frank-Kasper and quasicrystal assemblies except that the length of the supramolecular backbone is much longer in helical columns. A comparison of these systems with side-chain liquid crystals indicates that supramolecular dendrimers are stabilized by extended supramolecular backbone conformations. This result suggests pathways to molecularly engineer phase transitions of supramolecular dendrimers self-organized from crown conformations.