A novel low-molecular-mass gelator with a redox active ferrocenyl group: tuning gel formation by oxidation

A novel low-molecular-mass gelator containing a redox-active ferrocenyl group, cholesteryl glycinate ferrocenoylamide (CGF), was intentionally designed and prepared. It was demonstrated that the gelator gels 13 out of the 45 solvents tested. Scanning electron microscopy (SEM) measurements revealed that the gelator self-assembled into different supramolecular network structures in different gels. Chemical oxidation of the ferrocenyl residue resulted in phase transition of the gel from gel state to solution state. FTIR and (1)H NMR spectroscopy studies revealed that hydrogen bonding between the gelator molecules in the gel was one of the main driving forces for the formation of the gels.     

一种基于胆固醇的荧光小分子胶凝剂的合成及其胶凝行为

合成并表征了一种含7-硝基苯并-2-氧杂-1,3-二唑基(7-Nitrobenzo-2-oxa-1,3-diazol-4-yl)的胆固醇衍生物(NBD-C), 考察了其在30种溶剂中的胶凝行为. 实验结果表明, NBD-C对乙腈具有很强的胶凝作用, 且该凝胶体系具有显著的剪切触变性. 对干凝胶的显微分析发现, 在不同溶剂中, NBD-C具有不同的聚集结构. 红外光谱(FTIR)、核磁共振光谱(¹H NMR)和荧光光谱研究结果表明, 除了胆固醇的范德华堆积作用之外, 分子间氢键作用也是该化合物聚集的重要驱动力.     

Solvent‐Polarity‐Tuned Morphology and Inversion of Supramolecular Chirality in a Self‐Assembled Pyridylpyrazole‐Linked Glutamide Derivative: Nanofibers,Nanotwists, Nanotubes,and Microtubes

The self‐assembly of a low‐molecular‐weight organogelator into various hierarchical structures has been achieved for a pyridylpyrazole linked L ‐glutamide amphiphile in different solvents. Upon gel formation, supramolecular chirality was observed, which exhibited an obvious dependence on the polarity of the solvent. Positive supramolecular chirality was obtained in nonpolar solvents, whereas it was inverted into negative supramolecular chirality in polar solvents. Moreover, the gelator molecules self‐assembled into a diverse array of nanostructures over a wide scale range, from nanofibers to nanotubes and microtubes, depending on the solvent polarity. Such morphological changes could even occur for the xerogels in the solvent vapors. We found that the interactions between the pyridylpyrazole headgroups and the solvents could subtly change the stacking of the molecules and, hence, their self‐assembled nanostructures. This work exemplifies that organic solvents can significantly involve the gelation, as well as tune the structure and properties, of a gel.     

A Coformer Approach for Supramolecular Polymerization at High Concentrations

Insolubility of functional molecules caused by polymorphism sometimes poses limitations for their solution-based processing. Such a situation can also occur in the preparation processes of supramolecular polymers formed in a solution. An effective strategy to address this issue is to prepare amorphous solid states by introducing a “coformer” molecule capable of inhibiting the formation of an insoluble polymorph through co-aggregation. Herein, inspired by the coformer approach, we demonstrated a solubility enhancement of a barbiturate π-conjugated compound that can supramolecularly polymerize through six-membered hydrogen-bonded rosettes. Our newly synthesized supramolecular coformer molecule features a sterically demanding methyl group in the π-conjugated unit of the parent molecule. Although the parent molecule exhibits low solubility in nonpolar solvents due to the formation of a crystalline polymorph comprising a tape-like hydrogen-bonded array prior to the supramolecular polymerization, mixing with the coformer compound enhanced the solubility by inhibiting mesoscopic organization of the tapes. The two monomers were then co-polymerized into desired helicoidal supramolecular polymers through the formation of heteromeric rosettes.     

The remarkable role of hydrogen bond,halogen, and solvent effect on self-healing supramolecular gel

Self-healing supramolecular gels of low-molecular-weight (LMW) molecules are smart soft materials; however, the development of self-healing LMW gelator is still a challenging task because of the lack of in-depth studies about self-healing mechanisms of LMW gels and the solvent effect on gel properties. Therefore, herein a different perspective was used to study a family of D-gluconic acetal-based gelators with variable structural fragments in 14 different solvents, and a more detailed understanding of self-assembly and self-healing mechanism of supramolecular gels was attained. Based on the critical gelation concentration, phase transition temperature, and rheological data, A8 bearing an amide group in side chain and two chlorine atoms linked to benzene ring was found to be an outstanding gelator, which could form gels with good self-healing ability in a variety of solvents. Interestingly, A8 gel formed in n-BuOH demonstrates high transparency, good mechanical strength, self-supporting behavior, and great self-healing ability from mechanical damage. Based on the Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and theoretical calculation analysis, the self-assembly and self-healing mechanisms of A8 gel were proposed, indicating that a combination of hydrogen bonding and halogen effect was responsible for the efficient self-healing behavior of supramolecular gel. Furthermore, the analysis of solvent parameters indicated that the dispersion force of solvent favored gelators to self-assemble, hydrogen bonding donor ability of solvent mainly affected the formation of one-dimensional assembly, and hydrogen bonding receptor ability and polarity of solvent mainly influenced the supramolecular interactions among assemblies, significantly intervening the self-healing ability of gels. Overall, this study provides a new perspective to the understanding of gelator structure–property correlation in solvents and sheds light for future development of self-healing supramolecular gels.     

Amino acid derivatives of cholesterol as "latent" organogelators with hydrogen chloride as a protonation reagent

A series of low molecular weight organic gelator (LMOG) gel systems sensitive to alkaline/acidic stimuli was established by employing amino acid derivatives of cholesterol as "latent" gelators, which are cholesteryl glycinate (1), cholesteryl L-alaninate, cholesteryl D-alaninate, cholesteryl L-phenyl alaninate, and cholesteryl D-phenyl alaninate. The hydrochloric salts are denoted as 2, 3, 4, 5, and 6, respectively. For the 18 solvents tested, one proved to be a weak gelator and gels only two of the solvents. Its gelation ability, however, was greatly improved by bubbling HCl gas, which was produced by reaction of concentrated sulfuric acid with NaCl, through its solution owing to protonation of its amino group. It was demonstrated that the protonated form of it gelled 14 of the solvents tested. Further investigation revealed that the gels changed into solution with addition of any of the amines, including triethylamine (TEA), diethylamine, ethylenediamine, and NH3. The phase transition could be reversed by further introduction of the acidic gas. SEM measurements showed that 1 self-assembled into different supramolecular structures in different gels. Salt effect studies proved that electrostatic interaction is one of the driving forces for formation of the gels.     

Self‐Assembly of Three‐Dimensional Supramolecular Polymers through Cooperative Tetrathiafulvalene Radical Cation Dimerization

The self‐assembly of a new type of three‐dimensional (3D) supramolecular polymers from tetrahedral monomers in both organic and aqueous media is described. We have designed and synthesized two tetraphenylmethane derivatives T1 and T2 , both of which bear four tetrathiafulvalene (TTF) units. When the TTF units were oxidized to the radical cation TTF^.+, their pre‐organized tetrahedral arrangement remarkably enhanced their intermolecular dimerization, leading to the formation of new 3D spherical supramolecular polymers. The structure of the supramolecular polymers has been inferred on the basis of UV/Vis absorption, electron paramagnetic resonance, cyclic voltammetry, and dynamic light scattering (DLS) analysis, as well as by comparing these properties with those of the self‐assembled structures of mono‐, di‐, and tritopic control compounds. DLS experiments revealed that the spherical supramolecular polymers had hydrodynamic diameters of 68 nm for T1 (75 μM ) in acetonitrile and 105 nm for T2 (75 μM ) in water/acetonitrile (1:1). The 3D spherical structures of the supramolecular polymers formed in different solvents were also supported by SEM and AFM experiments.     

Formation of supramolecular polymers and discrete dimers of perylene bisimide dyes based on melamine-cyanurates hydrogen-bonding interactions

Melamine-linked perylene bisimide dyes (MPBIs) bearing an ethylene or trimethylene group as linker moieties were synthesized, and their self-aggregation and coaggregation with cyanurates through complementary triple hydrogen bonds have been investigated. UV/vis studies revealed that both the MPBIs self-assemble in nonpolar organic solvent through pi-pi stacking interaction between perylene cores, giving self-aggregates with nearly identical thermal stabilities. Upon addition of 1 equiv of cyanurate components, however, the stabilities of the resulting aggregates were dramatically changed between the two systems, suggesting the formation of different types of hydrogen-bonded supramolecular species. Dynamic light scattering and atomic force microscopic studies revealed that the system featuring ethylene linker moieties generates a discrete dimer of MPBI supported by two cyanurate molecules, whereas the system featuring trimethylene linker moieties affords extended supramolecular polymers hierarchically organizing into nanoscopic fibers. These results demonstrate that it is possible to obtain distinct supramolecular species by just changing the number of carbon atoms at the linker moieties of MPBI components. The present strategy for the fabrication of discrete or polymeric supramolecular assemblies should be applicable to other functional pi-conjugated molecules.     

一种含芘葡萄糖衍生物的合成及其胶凝行为

合成并表征了一种荧光活性小分子胶凝剂——芘磺酰基-丙二胺-葡萄糖(PSDAPG), 考察了其在36种常见溶剂中的胶凝行为. 结果发现, PSDAPG可使其中16种溶剂胶凝. 对癸醇, PSDAPG表现出罕见的超级胶凝能力, 室温下最低胶凝浓度(MGC)达7.0×10-4 g·mL-1. 此外, PSDAPG还是一种既可胶凝水又可胶凝有机溶剂的双性胶凝剂. 扫描电镜(SEM)、傅立叶变换红外光谱(FTIR)、核磁共振(1HNMR)和荧光光谱研究表明,在不同溶剂中, PSDAPG具有不同的聚集结构, 除了芘基之间的疏水π-π堆积作用外, 氢键作用是PSDAPG自发形成三维网络结构的重要驱动力. 实验研究还表明, 溶液态和凝胶态的PSDAPG荧光光谱均同时呈现芘的单体荧光和激基缔合物荧光光谱特征, 但两者的光谱形貌差异显著. 随凝胶的形成, 体系单体荧光发射增强, 激基缔合物荧光发射减弱,表明形成的三维网络结构阻碍了PSDAPG中芘单元的运动性, 使得以Birks途径形成激基缔合物的效率降低.     

H-bonding-driven gel formation of a phenylacetylene macrocycle

An amide-containing phenylacetylene macrocycle (PAM) has been synthesized and its gelation properties were studied in different solvents. Surprisingly, this macrocycle forms organogels at low concentration in many polar and apolar solvents. XRD and FTIR analysis suggest that this macrocycle forms stable supramolecular assemblies owing to H-bonding. Scanning electron microscopy analyses show the formation of bundles of nanofibrils, demonstrating the long-range organization of this material.     

Supramolecular polymers generated from heterocomplementary monomers linked through multiple hydrogen-bonding arrays--formation, characterization, and properties

Supramolecular polymers are described that are derived from the association of two homoditopic heterocomplementary monomers through sextuple hydrogen-bonding arrays. They form fibers and a variety of different materials depending on the conditions. The strong affinity of the DAD-DAD (D=donor, A=acceptor) hydrogen-bonding sites for double-faced cyanuric acid type wedges drives the supramolecular polymeric assembly in apolar and chlorinated organic solvents. The marked influence of stoichiometry, as well as end-capping and cross-linking agents upon fiber formation is revealed in solution and by electron microscopy (EM). The results further contribute to the development of a supramolecular polymer chemistry that comprises reversible polymers formed through recognition-controlled noncovalent connections between the molecular components. Such materials are, by nature, dynamic and present adaptive character in view of their ability to respond to external stimuli.     

Molecular-Recognition-Directed Self-Assembly of Pleated Sheets from 2-Aminopyrimidine Hydrogen-Bonding Motifs

The self-assembly of the 2,2′-diamino-5,5′-(dialkylmethylidene)methylenedipyrimidine derivatives 3a – c allows for the molecular-recognition-directed generation of pleated sheets as revealed by X-ray crystallographic analysis. The data provide insight into the interplay of the different structural and interactional features of the molecular components in the generation of the supramolecular assembly. The introduction of the adamantylidene group as in 3c leads to the dominance of the H-bonding factor and the resulting formation of a regular, fully interconnected array of pleated sheet type. The results suggest further manipulation of the interplay of the different factors to induce the self-assembly of other supramolecular architectures.     

A favorable, narrow, δ(h) Hansen-parameter domain for gelation of low-molecular-weight amino acid derivatives

In recent years, the design of new low-molecular-weight gelators (LMWGs) has attracted considerable attention because of the interesting supramolecular architectures as well as industrial applications. In this context, the role of the organic solvent in determining the organogelation behavior is a central question. Herein we report the results of a systematic study of the organogelation behavior of amino acid derivatives in a wide range of solvents to establish a relationship between the nature of the solvent and the formation of the gel. We highlight that the majority of the gelified solvents are aromatic, except for carbon tetrachloride and tetrachloroethylene. In addition, different parameters related to the nature of the solvent were considered and their influence on the physical properties of gelation was evaluated. The hydrogen-bonding Hansen parameter (δ(h)) allows us to draw a narrow favorable δ(h) domain for gelation in the range of 0.2-1.4 (cal cm(-3))(1/2). Furthermore, a general increase of the Hildebrand parameter (δ) leads to the formation of poor gels (small gelation numbers, GNs) in aromatic solvents. Scanning electron microscopy (SEM) revealed that the gels prepared from (l)-phenylalanine and (l)-leucine derivatives in different solvents are composed of an entangled 3D fibrillar network, the diameter of which is only slightly influenced by the nature of the solvent.     

Supramolecular Polymer Hydrogels from Bolaamphiphilic L‐Histidine and Benzene Dicarboxylic Acids: Thixotropy and Significant Enhancement of EuIII Fluorescence

Supramolecular polymers from the bolaamphiphilic L ‐histidine ( BolaHis ) and benzene dicarboxylic acids (o‐phthalic acid, OPA ; isophthalic acid, IPA and terephthalic acid, TPA ) were found to form hydrogels although neither of the single components could gel water. It was suggested that the hydrogen bond and ionic interactions among different imidazole and carboxylic acid groups are responsible for the formation of the supramolecular polymer as well as the hydrogel formation. Depending on the structures of the dicarboxylic acids, different behaviors of the gels were observed. The hydrogels from OPA / BolaHis and IPA / BolaHis showed thixotropic properties, that is, the hydrogel was destroyed by hand shaking and then slowly gelated again at room temperature. However, the hydrogels of TPA / BolaHis could not. Interestingly, when Eu^III was doped into IPA / BolaHis supramolecular polymers, very strong luminescence enhancement was observed. FT‐IR spectroscopies and XRD analysis revealed that the strong luminescence enhancement could be attributed to the matched supramolecular nanostructures, which render the correct binding and a good dispersion of Eu^III ions. The work offers a new approach for fabricating functional hydrogels through the supramolecular polymers.     

Driving Forces Controlling Host–Guest Recognition in Supercritical Carbon Dioxide Solvent

The formation of supramolecular host–guest complexes is a very useful and widely employed tool in chemistry. However, supramolecular chemistry in non‐conventional solvents such as supercritical carbon dioxide (scCO₂), one of the most promising sustainable solvents, is still in its infancy. In this work, we explored a successful route to the development of green processes in supercritical CO₂ by combining a theoretical approach with experiments. We were able to synthesize and characterize an inclusion complex between a polar aromatic molecule (benzoic acid) and peracetylated‐β‐cyclodextrin, which is soluble in the supercritical medium. This finding opens the way to wide, environmental friendly, applications of scCO₂ in many areas of chemistry, including supramolecular synthesis, reactivity and catalysis, micro and nano‐particle formation, molecular recognition, as well as enhanced extraction processes with increased selectivity.     

Light‐Controlled Formation of Vesicles and Supramolecular Organogels by a Cholesterol‐Bearing Amphiphilic Molecular Switch

A new responsive material composed of an amphiphilic light‐switchable dithienylethene unit functionalized with a hydrophobic cholesterol unit and a hydrophilic poly(ethylene glycol)‐modified pyridinium group has been designed. This unique single‐molecule system shows responsive light‐switchable self‐assembly in both water and organic solvents. Light‐triggered reversible vesicle formation in aqueous solutions is reported. The molecule shows a different behavior in apolar aromatic solvents, in which light‐controlled formation of organogel fibers is observed. The light‐triggered aggregation behavior of this molecule demonstrates that control of a supramolecular structure with light can be achieved in both aqueous and organic media and that this ability can be present in a single molecule. This opens the way toward the effective development of new strategies in soft nanotechnology for applications in controlled chemical release systems.     

Self-Assembly of Bowl-Shaped Naphthalimide-Annulated Corannulene

The self-assembly of a bowl-shaped naphthalimide-annulated corannulene of high solubility has been studied in a variety of solvents by NMR and UV/Vis spectroscopy. Evaluation by the anti-cooperative K₂-K model revealed the formation of supramolecular dimers of outstanding thermodynamic stability. Further structural proof for the almost exclusive formation of dimers over extended aggregates is demonstrated by atomic force microscopy (AFM) and diffusion ordered spectroscopy (DOSY) measurements as well as by theoretical calculations. Thus, herein we present the first report of a supramolecular dimer of an annulated corannulene derivative in solution and discuss its extraordinarily high thermodynamic stability with association constants up to >10⁶ M⁻¹ in methylcyclohexane, which is comparable to the association constants given for planar phthalocyanine and perylene bisimide dyes.     

Metallogels Self‐Assembled from Linear Rod‐Like Platinum Complexes: Influence of the Linkage

Two linear rod‐like platinum complexes, which only differed in the linkage, were prepared. They both self‐assemble into metallogels in nonpolar solvents; however, a very big contrast was observed. Unexpectedly, a much weaker gel was acquired upon replacing the ester linkage by an amide group. The intermolecular hydrogen bonding offered by the amide motif leads to a different stacking fashion and mechanism. The results demonstrated herein contribute to the rational design of metallogels as well as other functional supramolecular materials.     

Supramolecular polymerization and polymorphs of oligo(p-phenylene vinylene)-functionalized bis- and monoureas

Bis- and monoureas hybridized with the oligo(p-phenylene vinylene) (OPV) pi-electronic segment and 3,4,5-tridodecyloxyphenyl wedge were synthesized and their supramolecular polymerization in diluted solution, gel formation in concentrated solution, and liquid crystallinity in bulk state were investigated. Bisurea 1a featuring a hexamethylene linker showed the highest supramolecular polymerization ability and formed tapelike nanofibers that can gelate various organic solvents. On the other hand, bisurea 1b featuring a dodecamethylene linker and monourea 2 showed a lower degree of supramolecular polymerization, resulting in gel formations in a smaller variety of solvents. These results clearly reflect a high level of cooperativity between the two urea sites and the two OPV segments of 1a upon hydrogen-bonding and pi-pi stacking interactions, respectively. When the gels of 1a, 1b, and 2 were dried, all the compounds self-organized into multilamellar superstructures. Thermal treatment of these lamellae at high temperatures induces columnar liquid-crystalline mesophases as a result of microsegregation between the rigid OPV parts and the molten aliphatic wedges. These results demonstrate that the present molecular constituent is very useful for fabricating dye-based functional assemblies providing nanoscale pi-electronic fibers, and solvent-incorporated and bulk soft materials.