Controlling Aqueous Self‐Assembly Mechanisms by Hydrophobic Interactions

We report an innovative template‐assisted synthetic protocol for the selective functionalization of terminal triple bonds in oligophenyleneethynylenes (OPE) by pre‐organization in aqueous solution. By this approach, three new OPE‐based bolaamphiphiles substituted with hydrophilic poly(2‐ethyl‐2‐oxazoline) (PEtOx) chains of different length have been synthesized. The chain length was observed to strongly influence the aqueous supramolecular polymerization: bolaamphiphiles with longer hydrophilic chains aggregate into spherical nanoparticles in a stepwise fashion, whereas 2D anisotropic platelets are formed cooperatively if shorter PEtOx chains are used. Our results demonstrate that hydrophobic interactions can be strong enough to trigger cooperative effects in aqueous self‐assembly processes.     

Self‐Assembly and Disassembly of Vesicles as Controlled by Anion–π Interactions

Anion–π interactions have been widely studied as new noncovalent driving forces in supramolecular chemistry. However, self‐assembly induced by anion–π interactions is still largely unexplored. Herein we report the formation of supramolecular amphiphiles through anion–π interactions, and the subsequent formation of self‐assembled vesicles in water. With the π receptor 1 as the host and anionic amphiphiles, such as sodium dodecylsulfate (SDS), sodium laurate (SLA), and sodium methyl dodecylphosphonate (SDP), as guests, the sequential formation of host–guest supramolecular amphiphiles and self‐assembled vesicles was demonstrated by SEM, TEM, DLS, and XRD techniques. The intrinsic anion–π interactions between 1 and the anionic amphiphiles were confirmed by crystal diffraction, HRMS analysis, and DFT calculations. Furthermore, the controlled disassembly of the vesicles was promoted by competing anions, such as NO₃^?, Cl^?, and Br^?, or by changing the pH value of the medium.     

Formation of o‐Phenylenediamine Oligomers and their Self‐Assembly into One‐Dimensional Structures in Aqueous Medium

Summary: Uniform one‐dimensional (1D) structures of o‐phenylenediamine (oPD) oligomers are obtained by direct mix of AgNO₃ and oPD aqueous solutions at room temperature. The formation of the 1D structures involves two stages: (1) oxidation of oPD by AgNO₃, yielding individual oPD oligomers; and (2) self‐assembly of the oligomers, forming the 1D structures. Upon decreasing medium pH, the 1D structures can break‐apart to form individual oligomers, or vice versa. It is also found that both the concentration and molar ratio of reactants can influence the morphology of the structures thus formed.

Schematic illustration of the formation mechanism of 1D structures from oPD and AgNO₃, and energy‐dispersed spectrum of the precipitate.     

Supramolecular [60]Fullerene Liquid Crystals Formed By Self‐Organized Two‐Dimensional Crystals

Fullerene‐based liquid crystalline materials have both the excellent optical and electrical properties of fullerene and the self‐organization and external‐field‐responsive properties of liquid crystals (LCs). Herein, we demonstrate a new family of thermotropic [60]fullerene supramolecular LCs with hierarchical structures. The [60]fullerene dyads undergo self‐organization driven by π–π interactions to form triple‐layer two‐dimensional (2D) fullerene crystals sandwiched between layers of alkyl chains. The lamellar packing of 2D crystals gives rise to the formation of supramolecular LCs. This design strategy should be applicable to other molecules and lead to an enlarged family of 2D crystals and supramolecular liquid crystals.     

Counterions Control Whether Self‐Assembly Leads to Formation of Stable and Well‐Defined Unilamellar Nanotubes or Nanoribbons and Nanorods

Self‐assembly of the amphiphilic π‐conjugated carbenium ion ATOTA‐1⁺ in aqueous solution selectively leads to discrete and highly stable nanotubes or nanoribbons and nanorods, depending on the nature of the counterion (Cl^? vs. PF₆^?, respectively). The nanotubes formed by the Cl^? salt illustrate an exceptional example of a structural well‐defined (29±2 nm in outer diameter) unilamellar tubular morphology featuring π‐conjugated functionality and high stability and flexibility, in aqueous solution.     

Linear π‐Acceptor‐Templated Dynamic Clipping to Macrobicycles and [2]Rotaxanes

Cage me! A linear dumbbell‐shaped bipyridinium molecule can template cage formation around itself through sixfold imine bond formation to give an interlocked [2]rotaxane as the single product (see picture). This highly efficient [2+3] clipping occurs despite the symmetry mismatch between the template and the formed macrobicycle.

     

A Novel Ratiometric Oxygen Sensor Based On a Sextuple Hydrogen‐Bonding Self‐Assembly Molecular Heterodimer

A novel sextuple hydrogen‐bonding (HB) self‐assembly molecular heterodimer bearing an iridium complex as the indicator dye and two carbazoles as the reference dye, namely 6HB‐Irbt‐Cz , was synthesized, and its molecular structure was confirmed by ¹H NMR, ¹³CNMR, TOF‐MS and 2D NMR. Because of the inefficient energy transfer process between the carbazole and iridium complex units, 6HB‐Irbt‐Cz exhibits distinct ?uorescence/phosphorescence dual emission in neat film state. More importantly, the neat film sample of 6HB‐Irbt‐Cz could display linear ratiometric optical response toward oxygen in the full oxygen concentration range from 0 to 100 vol%, together with good stability, reversibility and rapid response‐recovery times. Note that this represents the first discovery of neat‐film‐based oxygen sensor capable of showing strictly linear ratiometric Stern‐Volmer behavior in the oxygen concentration of 0–100 vol%.     

Facile One‐Pot Synthesis of a Polyvinylpyrrolidone‐Based Self‐Crosslinked Fluorescent Film

A polyvinylpyrrolidone (PVP)‐based fluorescent film with stable optical properties is successfully prepared in one pot without any additive. The reaction mechanism of ring‐opening and self‐crosslinking of linear PVP is proposed and demonstrated. The morphologies and the nanostructures of the fluorescent film as well as the unmodified film are investigated. The dye is incorporated into the film networks via covalent linkages, thus leading to the highly stable optical properties. The facile and effective synthesis approach opens a new way for the design of other multi‐functional composite materials based on linear PVP.

     

DNA‐Assisted Self‐Assembly of Pyrene Foldamers

Folding in the tides : Upon hybridization, pyrene molecules assemble through interstrand stacking interactions to form double‐stranded, helical structures. Structural organization of the pyrene molecules is an intrinsic property of the oligoaryl part and takes place independently of the sequence of the attached DNA. Pyrene helicity is most pronounced in a bi‐segmental chimera, in which a DNA stem is present only at one end of the pyrene section.

     

Self‐Coupling of a 4‐H‐Butatrienylidene Tungsten Complex

Tungsten tryst : A 4‐H‐butatrienylidene complex of tungsten was successfully isolated and structurally characterized. It undergoes a unique self‐coupling, which leads to a dimer (see picture; P pink, O red) with a cross‐conjugated π system and with electrochemically and magnetically active metal centers.

     

Entropically Driven Self‐Assembly of Bolaamphiphilic Perylene Dyes in Water

The specific hydrophobic effect involved in the self‐assembly of a bolaamphiphilic perylene bisimide (PBI) dye bearing oligoethylene glycol (OEG) chains has been identified. In pure water, the self‐assembly is entropically driven and enthalpically disfavored, as explored by optical spectroscopy and isothermal titration calorimetry studies. Besides strong π–π interactions between the PBI units that are primarily of enthalpic nature, the major contribution to the self‐assembly is the gain of entropy by release of confined water molecules from the hydration shell of the hydrophilic OEG moieties. Both contributions favor self‐assembly, but their countervailing thermodynamic parameters are reflected in an uncommon temperature dependence, which can be inverted upon gradual addition of an organic cosolvent that makes the π–π interaction increasingly dominant.     

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.     

Self‐Healing Polymers via Supramolecular Forces

As polymers and polymeric materials are “the” smart invention and technological driving force of the 20th century, the quest for self‐healing or self‐repairing polymers is strong. The concept of supramolecular self‐healing materials relies on the use of noncovalent, transient bonds to generate networks, which are able to heal the damaged site, putting aspects of reversibility and dynamics of a network as crucial factors for the understanding and design of such self‐healing materials. This Review describes recent examples and concepts of supramolecular polymers based on hydrogen bonding, π–π interactions, ionomers, and coordinative bonds, thus convincingly discussing the advantages and versatility of these supramolecular forces for the design and realization of self‐healing polymers.     

Interplay between H‐Bonding and Preorganization in the Evolution of Self‐Assembled Systems

Cooperative π–π interactions and H‐bonding are frequently exploited in supramolecular polymerization; however, close scrutiny of their mutual interplay has been largely unexplored. Herein, we compare the self‐assembly behavior of a series of C₂‐ and C₃‐symmetrical oligophenyleneethynylenes differing in their amide topology (N‐ or C‐centered). This subtle structural modification brings about drastic changes in their photophysical and supramolecular properties, highlighting the reciprocal impact of H‐bonding vs. preorganization on the evolution and final outcome of supramolecular systems.     

Oligopeptide‐Assisted Self‐Assembly of Oligothiophenes: Co‐Assembly and Chirality Transfer

The biomolecule‐assisted self‐assembly of semiconductive molecules has been developed recently for the formation of potential bio‐based functional materials. Oligopeptide‐assisted self‐assembly of oligothiophene through weak intermolecular interactions was investigated; specifically the self‐assembly and chirality‐transfer behavior of achiral oligothiophenes in the presence of an oligopeptide with a strong tendency to form β‐sheets. Two kinds of oligothiophenes without (QT) or with (QTDA) carboxylic groups were selected to explore the effect of the end functional group on self‐assembly and chirality transfer. In both cases, organogels were formed. However, the assembly behavior of QT was quite different from that of QTDA. It was found that QT formed an organogel with the oligopeptide and co‐assembled into chiral nanostructures. Conversely, although QTDA also formed a gel with the oligopeptide, it has a strong tendency to self‐assemble independently. However, during the formation of the xerogel, the chirality of the oligopeptide can also be transferred to the QTDA assemblies. Different assembly models were proposed to explain the assembly behavior.     

Two‐Component Self‐Assembly: Hierarchical Formation of pH‐Switchable Supramolecular Networks by π–π Induced Aggregation of Ion Pairs

Two‐component self‐assembly is a promising approach to construct functional nanomaterials. Interaction of a flexible guanidiniocarbonyl pyrrole tetra‐cation ( 1 ) with naphthalene diimide dicarboxylic acid (NDIDC) in aqueous DMSO leads to the formation of supramolecular networks. First, the carboxylate groups of NDIDC bind to the guanidiniocarbonyl pyrrole cations of 1 in a 1:2 stoichiometry. Further π–π induced aggregation then leads to 3D networks, as established by dynamic light scattering studies (DLS), NMR, fluorescence titration, viscosity measurements, AFM, and TEM microscopy. Due to ion pairing, the resulting aggregates can be switched between the monomers and the aggregates reversibly using external stimuli like protonation or deprotonation. At high concentration, a stable colloidal solution is formed, which shows an extensive Tyndall effect. Increasing the concentrations even further leads to formation of a supramolecular gel.