Thermotropic Liquid Crystalline Research Articles

Structural Regulation of Microcellular Thermotropic Liquid Crystalline Polymer with Low‐Dielectric Properties During Supercritical Fluid Foaming Process

With the development of radio technology, 5G electronic equipment has higher requirements for materials. This has become an imperative matter to realize the controllable preparation of Thermotropic liquid crystal polyester (TLCP) foams with homogeneous microcellular. Accordingly, the foaming behavior of TLCP in isotropic state is investigated. TLCP foams are prepared by a one‐step rapid depressurization foaming method at different temperature pressures, with cell diameter in the range of 67.5–283.9 μm and the material density in the range of 0.37–0.25 g/cm3. In order to broaden the distribution of cell diameter and the density of TLCP foams, the mixture foaming agent of N2 and CO2 is used in foaming process. When mixture foaming agents are used, the cell diameter is widened to the range of 40.5–283.9 μm, and the material density is widened to the range of 0.70–0.25 g/cm3, which realizes the controllable preparation of cell diameter and material density of TLCP. The dielectric constant and dielectric loss of TLCP foams can be as low as 1.35‰ and 0.85‰ at 10 GHz, respectively. The structural regulation of low‐dielectric TLCP microcellular materials is achieved for the first time by way of varying the temperature, pressure, and co‐blowing agent ratio.

Controlling the Nematic Liquid Crystallinity of Cellulose Nanocrystals with an Alcohol Ethoxy Sulfonate Surfactant.

Cellulose nanocrystals (CNCs) are biobased colloidal nanorods that have unlocked new opportunities in the area of sustainable functional nanomaterials including structural films and coatings, biomedical devices, energy, sensing, and composite materials. While selective light reflection and sensing develop from the typical chiral nematic (cholesteric, Nem*) liquid crystallinity exhibited by CNCs, a wealth of technologies would benefit from a nematic liquid crystal (LC) with CNC uniaxial alignment. Therefore, this study answers the central question of whether surfactant complexation suppresses CNC chirality in favor of nematic lyotropic and thermotropic liquid crystallinity. Therein, we use a common surfactant having both nonionic and anionic blocks, namely, oligo(ethylene glycol) alkyl-3-sulfopropyl diether potassium salt (an alcohol ethoxy sulfonate (AES)). AES forms complexes with CNCs in toluene (a representative for nonpolar organic solvent) via hydrogen bonding with an AES' oligo(ethylene glycol) block. A sufficiently high AES weight fraction endows the dispersibility of CNC in toluene. Lyotropic liquid crystallinity with Schlieren textures containing two- and four-point brush defects is observed in polarized optical microscopy (POM), along with the suppression of the cholesteric fingerprint textures. The results suggest a nematic (Nem) phase in toluene. Moreover, thermotropic liquid crystallinity is observed by incorporating an excess of AES, in the absence of an additional solvent and upon mild heating. The Schlieren textures suggest a nematic system that undergoes uniaxial alignment under mild shear. Importantly, replacing AES with a corresponding nonionic surfactant does not lead to liquid crystalline properties, suggesting electrostatic structural control of the charged end group of AES. Overall, we introduce a new avenue to suppress CNC chirality to achieve nematic structures, which resolves the long-sought uniaxial alignment of CNCs in filaments, composite materials, and optical devices.

Phase diagram of a rigid rod system with attractive end groups

We present a molecular dynamics study into the thermotropic liquid crystalline phase behaviour of a coarse-grained model of a rigid bolaamphiphilic molecule. The model consists of 11 spherical beads held in a fixed linear arrangement, where the two opposing terminal beads are self-attracting, mimicking hydrophilic segments and the remaining internal beads, as well as cross-bead interactions, are softly repulsive, mimicking hydrophobic organic segments. The effect of the model’s end bead self-attraction strength on liquid crystalline phase behaviour is studied. Coexistence points between the smectic A, nematic and isotropic phases exhibited by the model are determined following a thermodynamic integration pathway, using equations of state constructed by multiple histogram reweighting of simulation data. Variants of Gibbs–Duhem integration are used to trace pressure–temperature coexistence curves. Under isobaric conditions, the effect of increasing the end-group self-attraction on the nematic–isotropic coexistence temperature is relatively small; however, the nematic phase stability is reduced at the expense of a significant increase in the smectic A–nematic coexistence temperature. Lower temperature simulations show the approximate smectic A–crystalline transition temperature to be only weakly dependent on the strength of the end-group self-attraction.

Non-covalent planarizing interactions yield highly ordered and thermotropic liquid crystalline conjugated polymers.

Controlling the multi-level assembly and morphological properties of conjugated polymers through structural manipulation has contributed significantly to the advancement of organic electronics. In this work, a redox active conjugated polymer, TPT-TT, composed of alternating 1,4-(2-thienyl)-2,5-dialkoxyphenylene (TPT) and thienothiophene (TT) units is reported with non-covalent intramolecular S⋯O and S⋯H-C interactions that induce controlled main-chain planarity and solid-state order. As confirmed by density functional theory (DFT) calculations, these intramolecular interactions influence the main chain conformation, promoting backbone planarization, while still allowing dihedral rotations at higher kinetic energies (higher temperature), and give rise to temperature-dependent aggregation properties. Thermotropic liquid crystalline (LC) behavior is confirmed by cross-polarized optical microscopy (CPOM) and closely correlated with multiple thermal transitions observed by differential scanning calorimetry (DSC). This LC behavior allows us to develop and utilize a thermal annealing treatment that results in thin films with notable long-range order, as shown by grazing-incidence X-ray diffraction (GIXD). Specifically, we identified a first LC phase, ranging from 218 °C to 107 °C, as a nematic phase featuring preferential face-on π-π stacking and edge-on lamellar stacking exhibiting a large extent of disorder and broad orientation distribution. A second LC phase is observed from 107 °C to 48 °C, as a smectic A phase featuring sharp, highly ordered out-of-plane lamellar stacking features and sharp tilted backbone stacking peaks, while the structure of a third LC phase with a transition at 48 °C remains unclear, but resembles that of the solid state at ambient temperature. Furthermore, the significance of thermal annealing is evident in the ∼3-fold enhancement of the electrical conductivity of ferric tosylate-doped annealed films reaching 55 S cm-1. More importantly, thermally annealed TPT-TT films exhibit both a narrow distribution of charge-carrier mobilities (1.4 ± 0.1) × 10-2 cm2 V-1 s-1 along with a remarkable device yield of 100% in an organic field-effect transistor (OFET) configuration. This molecular design approach to obtain highly ordered conjugated polymers in the solid state affords a deeper understanding of how intramolecular interactions and repeat-unit symmetry impact liquid crystallinity, solution aggregation, solution to solid-state transformation, solid-state morphology, and ultimately device applications.

Mechanical Properties of 3D-Printed Liquid Crystalline Polymers with Low and High Melting Temperatures.

Additive manufacturing allows for the production of complex components using various types of materials such as plastics, metals and ceramics without the need for molding tools. In the field of high-performance polymers, semi-crystalline polymers such as polyetheretherketone (PEEK) or amorphous polymers such as polyetherimide (PEI) are already successfully applied. Contrary to semi-crystalline and amorphous polymers, thermotropic liquid crystalline polymers (LCPs) do not change into an isotropic liquid during melting. Instead, they possess anisotropic properties in their liquid phase. Within the scope of this work, this special group of polymers was investigated with regard to its suitability for processing by means of fused filament fabrication. Using an LCP with a low melting temperature of around 280 °C is compared to processing an LCP that exhibits a high melting temperature around 330 °C. In doing so, it was revealed that the achievable mechanical properties strongly depend on the process parameters such as the direction of deposition, printing temperature, printing speed and layer height. At a layer height of 0.10 mm, a Young's modulus of 27.3 GPa was achieved. Moreover, by employing an annealing step after the printing process, the tensile strength could be increased up to 406 MPa at a layer height of 0.15 mm. Regarding the general suitability for FFF as well as the achieved uniaxial mechanical properties, the LCP with a low melting temperature was advantageous compared to the LCP with a high melting temperature.

Heating-Induced Switching to Hierarchical Liquid Crystallinity Combining Colloidal and Molecular Order in Zwitterionic Molecules.

Hierarchical self-assemblies of soft matter involving triggerable or switchable structures at different length scales have been pursued toward multifunctional behaviors and complexity inspired by biological matter. They require several and balanced competing attractive and repulsive interactions, which provide a grand challenge in particular in the "bulk" state, i.e., in the absence of plasticizing solvents. Here, we disclose that zwitterionic bis-n-tetradecylphosphobetaine, as a model compound, shows a complex thermally switchable hierarchical self-assembly in the solvent-free state. It shows polymorphism and heating-induced reversible switching from low-temperature molecular-level assemblies to high-temperature hierarchical self-assemblies, unexpectedly combining colloidal and molecular self-assemblies, as inferred by synchrotron small-angle X-ray scattering (SAXS). The high-temperature phase sustains birefringent flow, indicating a new type of hierarchical thermotropic liquid crystallinity. The high-temperature colloidal-level SAXS reflections suggest indexation as a 2D oblique pattern and their well-defined layer separation in the perpendicular direction. We suggest that the colloidal self-assembled motifs are 2D nanoplatelets formed by the lateral packing of the molecules, where the molecular packing frustration between the tightly packed zwitterionic moieties and the coiled alkyl chains demanding more space limits the lateral platelet growth controlled by the alkyl stretching entropy. An indirect proof is provided by the addition of plasticizing ionic liquids, which relieve the ionic dense packings of zwitterions, thus allowing purely smectic liquid crystallinity without the colloidal level order. Thus, molecules with a simple chemical structure can lead to structural hierarchy and tunable complexity in the solvent-free state by balancing the competing long-range electrostatics and short-range nanosegregations.

Amphotropic liquid crystal polyacetylene derivative bearing pyrimidine type mesogen

An amphotropic liquid crystal polyacetylene derivative with pyrimidine–type two-ringed mesogenic core, exhibiting both thermotropic and lyotropic liquid crystallinity, was synthesized in this study. The polyacetylene derivative showed a lyotropic liquid crystal in d-limonene. The cis configuration of the main chain was confirmed via 1H NMR. Heat treatment induced cis–trans isomerization of the as-prepared polymer. Gas-phase iodine doping of the polymer initiated a chemical interaction between the polyene and iodine, acting as an electron acceptor, generating charge carriers (radical cations, solitons) detected with the electron spin resonance spectroscopy. Moreover, gas phase doping of the polymer induced cis–trans isomerization.

Thermotropic liquid crystalline 4-(Nonyloxy) benzoic acid: Phase transition temperatures, thermodynamic characterization, and separation of structural isomers

Thermotropic liquid crystalline 4-(Nonyloxy) benzoic acid: Phase transition temperatures, thermodynamic characterization, and separation of structural isomers

Thermotropic Colloidal Liquid‐Crystalline Hydroxyapatite Nanorod Hybrids Containing a Forklike Mesogen

AbstractWe here report the development of new thermotropic colloidal liquid‐crystalline (LC) organic/inorganic hybrids consisting of a hydroxyapatite (HAp)/poly(acrylic acid) (PAA) nanorod and a dendritic forklike mesogen. Complexation of the HAp/PAA nanorod covered with negatively charged PAA and a cationic forklike mesogen through electrostatic interactions and cation metathesis results in the surface modification of the HAp/PAA nanorod with the forklike mesogen. While the HAp/PAA nanorod forms a lyotropic colloidal LC phase in the aqueous dispersion, the HAp/PAA nanorod modified with the forklike mesogen exhibits thermotropic colloidal LC phases in the solvent‐free states. The biomineral‐based organic/inorganic colloidal liquid crystals exhibiting thermotropic LC properties have potential for the development of new stimuli‐responsive sustainable materials.

Effects of Dispersed Carbon Nanotubes and Emerging Supramolecular Structures on Phase Transitions in Liquid Crystals: Physico-Chemical Aspects

The current state of the study of different liquid crystalline (LC) systems doped with carbon nanotubes (CNTs) is discussed. An attempt is endeavored to outline the state-of-the-art technology that has emerged after two past decades. Systematization and analysis are presented for the integration of single- and multi-walled carbon nanotubes in thermotropic (nematic, smectic, cholesteric, ferroelectric, etc.) and lyotropic LCs. Special attention is paid to the effects of alignment and supramolecular organization resulting from orientational coupling between CNTs and the LC matrix. The effects of the specific inter-molecular and inter-particle interactions and intriguing microstructural, electromagnetic, percolation, optical, and electro-optical properties are also discussed.

Phase Equilibria and Critical Behavior in Nematogenic MBBA-Isooctane Monotectic-Type Mixtures.

The transition from the isotropic (I) liquid to the nematic-type (N) uniaxial phase appearing as the consequence of the elongated geometry of elements seems to be a universal phenomenon for many types of suspensions, from solid nano-rods to biological particles based colloids. Rod-like thermotropic nematogenic liquid crystalline (LC) compounds and their mixtures with a molecular solvent (Sol) can be a significant reference for this category, enabling insights into universal features. The report presents studies in 4'-methoxybenzylidene-4-n-butylaniline (MBBA) and isooctane (Sol) mixtures, for which the monotectic-type phase diagram was found. There are two biphasic regions (i) for the low (TP1, isotropic liquid-nematic coexistence), and (ii) high (TP2, liquid-liquid coexistence) concentrations of isooctane. For both domains, biphasic coexistence curves' have been discussed and parameterized. For TP2 it is related to the order parameter and diameter tests. Notable is the anomalous mean-field type behavior near the critical consolute temperature. Regarding the isotropic liquid phase, critical opalescence has been detected above both biphasic regions. For TP2 it starts ca. 20 K above the critical consolute temperature. The nature of pretransitional fluctuations in the isotropic liquid phase was tested via nonlinear dielectric effect (NDE) measurements. It is classic (mean-field) above TP1 and non-classic above the TP2 domain. The long-standing problem regarding the non-critical background effect was solved to reach this result.

Statement of Retraction: Thermotropic Liquid Crystalline Phases in Binary Mixture of Nonmesogenic Compounds

Statement of Retraction: Thermotropic Liquid Crystalline Phases in Binary Mixture of Nonmesogenic Compounds

Effects of Mesogenic Cycloaliphatic Units on the Microstructure and Properties of Thermotropic Liquid Crystalline Polyesters

AbstractWe report the synthesis and structure‐property relationship of new thermotropic liquid crystalline polyesters (TLCPs) with different mesogenic cycloaliphatic unit content in the mainchain. For this purpose, a series of TLCPs composed of three different repeating units based on 4‐hydroxybenzoic acid (HBA, 75.0 mol%), 2‐hydroxy‐6‐naphthoic acid (HNA, 25.0–15.0 mol%), and terephthalic acid/1,4‐cyclohexanedimethanol (TPA/CHDM, 0.0–10.0 mol%) were synthesized via two‐step bulk polymerization. The structure, thermal and mechanical properties of the TLCPs were investigated by considering the effects of size and content of TPA/CHDM‐derived repeating units, in comparison to HNA‐based repeating units. Infrared spectroscopic data showed that TPA/CHDM‐derived repeating units were successfully incorporated into HBA/HNA‐based TLCPs. The polarized optical and electron microscopic images revealed the existence of thermotropic liquid crystalline features and associated fibrillar structures for all TLCPs. The melting temperatures of the TLCPs decreased with increasing the TPA/CHDM‐based repeating units, whereas the glass transition temperature increased, which is due to the trade‐off effect of the segmental mobility restriction in the amorphous phase and the destruction of the thermotropic liquid crystalline phase by the introduction of TPA/CHDM‐derived repeating units in the TLCP mainchain. In addition, the maximum elastic storage modulus was attained for the TLCP with 2.5 mol% TPA/CHDM‐derived repeating units.

Synthesis and structure-property relationship of thermotropic liquid crystalline polyesters containing thiophene-aromatic and cycloaliphatic moieties

ABSTRACT We report the structure and property characterization of a series of thermotropic liquid crystalline polyesters (TLCPs) composed of three different repeating units based on 1,4-hydroxybenzoic acid (HBA), 6-hydroxy-2-naphthoic acid (HNA), and 2,5-thiophenedicarboxylic acid/1,4-cyclohexanedimethanol (TDCA/CHDM), which are synthesized through two-step melt polymerization. The effect of the TDCA/CHDM-based repeating unit (0.0–10.0 mol%) on the structure, thermal and mechanical properties of the TLCPs with 75.0 mol% HBA and 25.0–15.0 mol% HNA were investigated. The polarized optical and electron microscopic images confirmed the presence of thermotropic liquid crystalline and fibrillar structures for all synthesized TLCPs. The glass transition and melting temperatures as well as the crystallinity index of the TLCPs were found to increase with increment of the TDCA/CHDM unit up to 5.0 mol% due to the improved interchain packing, but they decreased at higher amounts of 7.5–10.0 mol% TDCA/CHDM units owing to the enhanced flexibility by the cyclohexylene ring and the mismatching in the length between HNA and TCDA/CHDM units. In addition, there was a crystal lattice transition of TLCPs from pseudo-hexagonal to orthorhombic phases. Although the thermal decomposition temperature and elastic storage moduli of the TLCPs decreased with the amount of the TDCA/CHDM unit, all TLCPs remained stable up to 300°C and had excellent elastic moduli above 4.1 GPa at 50°C.

Effect of the Molecular Structure Change of a Matrix Polymer (Nylon 6) on the Deformation of Dispersed Phase (a Thermotropic Liquid Crystalline Polymer) Droplets in Shear Flow.

In this work, we investigated the effect of a change in the molecular structure and ensuing molar mass change of a matrix polymer (polyamide 6, Ny 6) on droplet deformation of a dispersed thermotropic liquid crystalline polymer (TLCP, a poly(ester amide)) in shear flow. This study focuses on a total capillary number (the sum of the shear capillary number and the elasticity capillary number) and the viscosity ratio between the TLCP and Ny 6, for the morphological development and mechanical performance of TLCP/Ny 6 blends. In contrast to Ny 6, which has a lower melt viscosity than the TLCP melt, a modified Ny 6 (m-Ny 6) with ca. 2 orders higher melt viscosity than that of Ny 6 at a shear rate of 1 s–1 was found to facilitate the deformation of the TLCP phase. A total capillary number was defined to characterize the viscoelasticity effect on droplet deformation in the blend system. The first normal stress difference obtained from the viscosity curve using Steller’s method was used for the evaluation of the elasticity capillary number. The total capillary number for the Ny 6 blend was far less than the critical capillary number and was insufficient for the dispersed TLCP droplets to be deformed. The shear capillary number of the m-Ny 6 blend was greater than the critical capillary number but was still insufficient for droplet deformation into fibril shapes. The total capillary number, including the elastic capillary number, was sufficiently greater than the critical capillary number for deformation of the dispersed TLCP droplets. Morphological observations and a comparison with the theoretical work confirmed the importance of the viscoelasticity of the melt in the immiscible Ny 6/TLCP blends for in situ composite fabrication in shear flow. Both the high viscosity and the first normal stress difference of m-Ny 6 promote the deformation and fibrillation of the dispersed TLCP droplets.

Reaction Mechanism Study on Transesterification in Synthesis of Thermotropic Liquid Crystalline Polymer Catalyzed by Zinc(Ii) Carboxylate: A Combination of Dft and Kinetics Analyses

Reaction Mechanism Study on Transesterification in Synthesis of Thermotropic Liquid Crystalline Polymer Catalyzed by Zinc(Ii) Carboxylate: A Combination of Dft and Kinetics Analyses

Self-assembled materials from cellulose nanocrystals conjugated with a thermotropic liquid crystalline moiety.

Manipulating molecular and supramolecular interactions within cellulose nanocrystals (CNCs) to introduce different levels of assemblies combined with multiple functionalities is required for the development of degradable smart materials from renewable resources. To attain hierarchical structures and stimuli-responsive properties, a new class of liquid crystalline cellulosic hybrid materials is synthesized. Herein, main-chain rigid-rod-like oxidized cellulose (CNC-COOH) is prepared from a Cellulose Whatman filter paper (Cellulose W.P.) by acid hydrolysis and oxidized using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO). Thermotropic LC molecule, 4-cyano-4'-hydroxybiphenyl with a 12-methylene spacer (CB12-OH) is grafted onto the carboxylic acid group of CNC-COOH via Steglich esterification. The liquid crystalline functionalized CNCs cellulose nanocrystals (CNC-COO-CB12) are readily soluble in DMSO and ionic liquids. The extent of functionalization and structure of CNC-COO-CB12 are confirmed by solution-state 1H NMR and supported by other characterization techniques. We investigate the interplay of liquid crystalline orientational order of CNCs and cyanobiphenyl (CB12), and the supramolecular hydrogen bonding of CNCs within CNC-COO-CB12 and compare it with CNC-COOH. The introduction of thermotropic CB12 side chains onto rigid-rod CNCs shows the exclusive formation of smectic mesophases from the assemblies of CB12 with the absence of the cholesteric mesophase typically observed from CNC-COOH as verified by temperature-controlled SAXS (T-SAXS). This is further verified by UV-visible and SEM studies that show CNC-COO-CB12 forms smectic domains while CNC-COOH forms a visible light reflecting cholesteric mesophase in dried films. Thus, the interplay of liquid crystalline order of CNCs and CB12 and supramolecular hydrogen bonding of CNCs results in ordered, smectic-mesostructured CNCs for use in stimuli-responsive functional materials.

Hybrid Liquid-Crystalline Electrolytes with High-Temperature-Stable Channels for Anhydrous Proton Conduction.

Modern electrochemical and electronic devices require advanced electrolytes. Liquid crystals have emerged as promising electrolyte candidates due to their good fluidity and long-range order. However, the mesophase of liquid crystals is variable upon heating, which limits their applications as high-temperature electrolytes, e.g., implementing anhydrous proton conduction above 100 °C. Here, we report a highly stable thermotropic liquid-crystalline electrolyte based on the electrostatic self-assembly of polyoxometalate (POM) clusters and zwitterionic polymer ligands. These electrolytes can form a well-ordered mesophase with sub-10 nm POM-based columnar domains, attributed to the dynamic rearrangement of polymer ligands on POM surfaces. Notably, POMs can serve as both electrostatic cross-linkers and high proton conductors, which enable the columnar domains to be high-temperature-stable channels for anhydrous proton conduction. These nanochannels can maintain constant columnar structures in a wide temperature range from 90 to 160 °C. This work demonstrates the unique role of POMs in developing high-performance liquid-crystalline electrolytes, which can provide a new route to design advanced ion transport systems for energy and electronic applications.

Synthesis of novel liquid crystal compound and study of its behavior as corrosion inhibitor for mild steel in acidic medium (1 M) HCl

Novel liquid crystal (LC) namely, (E)-N-hexadecyl-4-(((4-iodophenyl)imino)methyl)-N,N-dimethylbenzenaminium bromide (IC16) was prepared and characterized by Fourier transform infrared (FT-IR), 1H nuclear magnetic resonance spectra, and mass spectrometry. The thermotropic liquid-crystalline (LC) properties were examined by differential scanning calorimetry (DSC). The prepared LC was evaluated as corrosion inhibitor with non-electrochemical and electrochemical methods. Electrochemical methods include potentiodynamic polarization (PP), electrochemical impedance spectroscopy (EIS), electrochemical frequency modulation (EFM). Non electrochemical method measuring with different temperature. The results showed that the synthesized compound possesses liquid crystal properties and it has a significant efficiency as anticorrosion (91%–97%). The adsorption of IC16 compound on mild steel surface was found to follow the Langmuir isotherm.

Anhydrous Proton Transport within Phosphonic Acid Layers in Monodisperse Telechelic Polyethylenes

Polymers bearing phosphonic acid groups have been proposed as anhydrous proton-conducting membranes at elevated operating temperatures for applications in fuel cells. However, the synthesis of phosphonated polymers and the control over the nanostructure of such polymers is challenging. Here, we report the straightforward synthesis of phosphonic acid-terminated, long-chain aliphatic materials with precisely 26 and 48 carbon atoms (C26PA2 and C48PA2). These materials combine the structuring ability of monodisperse polyethylenes with the ability of phosphonic acid groups to form strong hydrogen-bonding networks. Anhydride formation is absent so that charge carrier loss by a condensation reaction is avoided even at elevated temperatures. Below the melting temperature (Tm), both materials exhibit a crystalline polyethylene backbone and a layered morphology with planar phosphonic acid aggregates separated by 29 and 55 Å for C26PA2 and C48PA2, respectively. Above Tm, the amorphous polyethylene (PE) segments coexist with the layered aggregates. This phenomenon is especially pronounced for the C26PA2 and is identified as a thermotropic smectic liquid crystalline phase. Under these conditions, an extraordinarily high correlation length (940 Å) along the layer normal is observed, demonstrating the strength of the hydrogen bond network formed by the phosphonic acid groups. The proton conductivity in both materials in the absence of water reaches 10-4 S/cm at 150 °C. These new precise phosphonic acid-based materials illustrate the importance of controlling the chemistry to form self-assembled nanoscale aggregates that facilitate rapid proton conductivity.