Modulating self-assembly and polymorph transitions in bisdendronized squaramides.

Supramolecular self-assembly is an advanced approach for constructing ordered nanoscale architectures with broad applications. While the principles of supramolecular polymerization have been thoroughly explored in artificial small molecules, polymer transformations remain barely explored, likely due to the lack of suitable reference models presenting well-defined and reversible transitions between aggregates. In this study, we introduce a series of bisdendronized squaramides (SQs) 1-3, showcasing complex self-assembly behaviours involving four distinct aggregates, three different interaction patterns, and various thermodynamically controlled polymorph transformations.

Two-Dimensional Supramolecular Polymorphism in Cyanine H- and J-Aggregates.

We designed a new cyanine dye 1, with two pedant rod-like groups, capable of forming two distinct two-dimensional (2D) supramolecular polymorphs in methylcyclohexane; an H-type aggregate (Agg-H) and a J-type aggregate (Agg-J). Importantly, these two polymorphs were not accessed through polymerization events, and instead through the thermal transformation of a third particle-like polymorph (Agg-H) formed by the anti-cooperative assembly of 1. While Agg-H is generated upon cooling the solution of Agg-H by a thermoreversible polymorph transition, the Agg-J was obtained through a hidden pathway by combining sonication and cooling to the Agg-H solution.

Isothermal Phase Transitions in Liquid Crystals Driven by Dynamic Covalent Chemistry.

The dynamic nature of calamitic liquid crystals is exploited to perform isothermal phase transitions driven by dynamic covalent chemistry. For this purpose, nematic (N) arrays based on aldehyde 1 were treated with different amines (A-E) in an on-surface process, which resulted in different isothermal phase transitions. These phase transformations were caused by in situ imination reactions and are dependent on the nature of the added amine.

Two-Dimensional Supramolecular Polymerization of a Bis-Urea Macrocycle into a Brick-Like Hydrogen-Bonded Network.

We report on a dendronized bis-urea macrocycle 1 self-assembling via a cooperative mechanism into two-dimensional (2D) nanosheets formed solely by alternated urea-urea hydrogen bonding interactions. The pure macrocycle self-assembles in bulk into one-dimensional liquid-crystalline columnar phases. In contrast, its self-assembly mode drastically changes in CHCl or tetrachloroethane, leading to 2D hydrogen-bonded networks.

Pathway-Controlled Aqueous Supramolecular Polymerization via Solvent-Dependent Chain Conformation Effects.

Solute-solvent interactions play a critical role in multiple fields, including biology, materials science, and (physical) organic, polymer, and supramolecular chemistry. Within the growing field of supramolecular polymer science, these interactions have been recognized as an important driving force for (entropically driven) intermolecular association, particularly in aqueous media. However, to date, solute-solvent effects remain poorly understood in the context of complex self-assembly energy landscapes and pathway complexity.

Bioinspired crowding directs supramolecular polymerisation.

Crowding effects are crucial to maintaining functionality in biological systems, but little is known about their role in analogous artificial counterparts. Within the growing field of supramolecular polymer science, crowding effects have hitherto remained underappreciated. Herein, we show that crowding effects exhibit strong and distinct control over the kinetics, accessible pathways and final outcomes of supramolecular polymerisation processes.

Anticooperative Supramolecular Oligomerization Mediated by V-Shaped Monomer Design and Unconventional Hydrogen Bonds.

After more than three decades of extensive investigations on supramolecular polymers, strategies for self-limiting growth still remain challenging. Herein, we exploit a new V-shaped monomer design to achieve anticooperatively formed oligomers with superior robustness and high luminescence. In toluene, the monomer-oligomer equilibrium is shifted to the monomer side, enabling the elucidation of the molecular packing modes and the resulting (weak) anticooperativity.

Thermoreversible Polymorph Transitions in Supramolecular Polymers of Hydrogen-Bonded Squaramides.

Hydrogen-bonded squaramide (SQ) supramolecular polymers exhibit uncommon thermoreversible polymorph transitions between particle- and fiber-like nanostructures. SQs 1-3, with different steric bulk, self-assemble in solution into particles (AggI) upon cooling to 298 K, and SQs 1 and 2, with only one dendronic group, show a reversible transformation into fibers (AggII) by further decreasing the temperature to 288 K. Nano-DSC and UV/Vis studies on SQ 1 reveal a concentration-dependent transition temperature and ΔH for the AggI-to-AggII conversion, while the kinetic studies on SQ 2 indicate the on-pathway nature of the polymorph transition.

Anti-cooperative Self-Assembly with Maintained Emission Regulated by Conformational and Steric Effects.

Herein, we present a strategy to enable a maintained emissive behavior in the self-assembled state by enforcing an anti-cooperative self-assembly involving weak intermolecular dye interactions. To achieve this goal, we designed a conformationally flexible monomer unit 1 with a central 1,3-substituted (diphenyl)urea hydrogen bonding synthon that is tethered to two BODIPY dyes featuring sterically bulky trialkoxybenzene substituents at the meso-position. The competition between attractive forces (H-bonding and aromatic interactions) and destabilizing effects (steric and competing conformational effects) limits the assembly, halting the supramolecular growth at the stage of small oligomers.

Supramolecular polymerization of electronically complementary linear motifs: anti-cooperativity by attenuated growth.

Anti-cooperative supramolecular polymerization by attenuated growth exhibited by self-assembling units of two electron-donor benzo[1,2-:4,5-']dithiophene (BDT) derivatives (compounds 1a and 1b) and the electron-acceptor 4,4-difluoro-4-bora-3,4-diaza--indacene (BODIPY) (compound 2) is reported. Despite the apparent cooperative mechanism of 1 and 2, AFM imaging and SAXS measurements reveal the formation of small aggregates that suggest the operation of an anti-cooperative mechanism strongly conditioned by an attenuated growth. In this mechanism, the formation of the nuclei is favoured over the subsequent addition of monomeric units to the aggregate, which finally results in short aggregates.

Advanced Functional Liquid Crystals.

Liquid crystals have been intensively studied as functional materials. Recently, integration of various disciplines has led to new directions in the design of functional liquid-crystalline materials in the fields of energy, water, photonics, actuation, sensing, and biotechnology. Here, recent advances in functional liquid crystals based on polymers, supramolecular complexes, gels, colloids, and inorganic-based hybrids are reviewed, from design strategies to functionalization of these materials and interfaces.

Unveiling the Role of Hydrogen Bonds in Luminescent N-Annulated Perylene Liquid Crystals.

We report the liquid-crystalline (LC) and luminescent properties of a series of N-annulated perylenes (1-4) in whose molecular structures amide and ester groups alternate. We found that the LC properties of these compounds not only depend on the number of hydrogen-bonding units, but also on the relative position of the amide linkers in the molecule. The absence of amide groups in compound 1 leads to no LC properties, whereas four amide groups induce the formation of a wide temperature range columnar hexagonal phase in compound 4.

Dual role of silver in a fluorogenic -squaraine probe based on Ag(I)-π interactions.

In the presence of Ag(i), the monoanion of cyano-N-squaraine (I) generates an intense fluorescence turn-on response. Experimental evidence and DFT calculations reveal a sequence of deprotonation-coordination events in which the Ag(i) ions play a dual role as a Lewis acid and coordinating metal. The observed effect is highly selective for Ag(i) compared to other metals.

Influence of the Z/E Isomerism on the Pathway Complexity of a Squaramide-Based Macrocycle.

The rising interest on pathway complexity in supramolecular polymerization has prompted the finding of novel monomer designs able to stabilize kinetically trapped species and generate supramolecular polymorphs. In the present work, the exploitation of the Z/E (geometrical) isomerism of squaramide (SQ) units to produce various self-assembled isoforms and complex supramolecular polymerization pathways in methylcyclohexane/CHCl mixtures is reported for the first time. This is achieved by using a new bissquaramidic macrocycle (MSq) that self-assembles into two markedly different thermodynamic aggregates, AggA (discrete cyclic structures) and AggB (fibrillar structures), depending on the solvent composition and concentration.

Thermodynamic insights into the entropically driven self-assembly of amphiphilic dyes in water.

Self-assembly of amphiphilic dyes and π-systems are more difficult to understand and to control in water compared to organic solvents due to the hydrophobic effect. Herein, we elucidate in detail the self-assembly of a series of archetype bolaamphiphiles bearing a naphthalene bisimide (NBI) π-core with appended oligoethylene glycol (OEG) dendrons of different size. By utilizing temperature-dependent UV-vis spectroscopy and isothermal titration calorimetry (ITC), we have dissected the enthalpic and entropic parameters pertaining to the molecules' self-assembly.

Self-assembly of amphiphilic aryl-squaramides in water driven by dipolar π-π interactions.

Squaramides are versatile compounds with a great capacity to interact via non-covalent interactions and therefore of interest for the development of supramolecular systems and functional materials. In the present work, a new series of aryl-squaramide amphiphiles (1-5) were prepared to form supramolecular polymers in water. Interestingly, only compounds 1 and 2 that contain electron-deficient aryl groups are capable of forming hydrogels (∼10 M) upon treatment with a base (NaOH or PBS).

Development of Plasmonic Chitosan-Squarate Hydrogels via Bioinspired Nanoparticle Growth.

We report on the bioinspired growth of gold nanoparticles (GNPs) in biocompatible hydrogels to develop plasmonic hybrid materials. The new hydrogel () is prepared from chitosan and diethylsquarate and is formed via noncovalent interactions rising between the in situ formed ionic squaric acid derivatives and chitosan. Interestingly, when the hydrogel is prepared in the presence of HAuCl, GNPs with controlled sizes between 15 and 50 nm are obtained, which are homogeneously distributed within the plasmonic hydrogels ().

Surface Modification of Pseudoboehmite-Coated Aluminum Plates with Squaramic Acid Amphiphiles.

The functionalization of interfaces has become very important for the protection or modification of metal (metal oxides) surfaces. The functionalization of aluminum is particularly interesting because of its relevance in fabricating components for electronic devices. In this work, the utilization of squaramic acids for the functionalization of aluminum substrates is reported for the first time.

Anisotropic microfibres of a liquid-crystalline diketopyrrolopyrrole by self-assembly-assisted electrospinning.

Electrospinning is a well-established technique for the preparation of nanofibres from polymer solution or melt, however it is rarely applied for small molecules. Here we report a unique example of a liquid-crystalline (LC) diketopyrrolopyrrole (DPP) dye that was successfully used for electrospinning. Micrometric fibres with anisotropic alignment of DPP dye were produced by this process as shown by polarized optical microscopy and selected area electron diffraction.

Hydrogen-bonded perylene bisimide J-aggregate aqua material.

A new twelvefold methoxy-triethyleneglycol-jacketed tetraphenoxy-perylene bisimide () amphiphile was synthesized that self-assembles into two types of supramolecular aggregates in water: red-coloured aggregates of low order and with weak exciton coupling among the PBIs and blue-coloured strongly coupled J-aggregates consisting of a highly ordered hydrogen-bonded triple helix of PBIs. At room temperature this PBI is miscible with water at any proportions which enables the development of robust dye aggregates in solution, in hydrogel states and in lyotropic liquid crystalline states. In the presence of 60-95 wt% water, self-standing coloured hydrogels exhibit colour changes from red to blue accompanied by a fluorescence light-up in the far-red region upon heating in the range of 30-50 °C.

Self-assembly of multi-stranded perylene dye J-aggregates in columnar liquid-crystalline phases.

Many discoid dyes self-assemble into columnar liquid-crystalline (LC) phases with packing arrangements that are undesired for photonic applications due to H-type exciton coupling. Here, we report a series of crystalline and LC perylene bisimides (PBIs) self-assembling into single or multi-stranded (two, three, and four strands) aggregates with predominant J-type exciton coupling. These differences in the supramolecular packing and optical properties are achieved by molecular design variations of tetra-bay phenoxy-dendronized PBIs with two N-H groups at the imide positions.

Development of Nanostructured Water Treatment Membranes Based on Thermotropic Liquid Crystals: Molecular Design of Sub-Nanoporous Materials.

Supply of safe fresh water is currently one of the most important global issues. Membranes technologies are essential to treat water efficiently with low costs and energy consumption. Here, the development of self-organized nanostructured water treatment membranes based on ionic liquid crystals composed of ammonium, imidazolium, and pyridinium moieties is reported.

Diketopyrrolopyrrole Columnar Liquid-Crystalline Assembly Directed by Quadruple Hydrogen Bonds.

A diketopyrrolopyrrole (DPP) dye self-assembles via a unique hydrogen-bonding motif into an unprecedented columnar liquid-crystalline (LC) structure. X-ray and polarized FTIR experiments reveal that the DPPs organize into a one-dimensional assembly with the chromophores oriented parallel to the columnar axis. This columnar structure is composed of two π-π-stacked DPP dimers with mirror-image configurations that stack alternately through quadruple hydrogen bonding by 90° rotation.

Self-Assembled Liquid-Crystalline Ion Conductors in Dye-Sensitized Solar Cells: Effects of Molecular Sensitizers on Their Performance.

Dye-sensitized solar cells employing nonvolatile liquid-crystalline (LC) electrolytes that form nanostructures capable of efficient ion transport are reported. The LC electrolyte consists of a cyclic carbonate-functionalized mesogen and an iodide-based ionic liquid that nanosegregates into lamellar structures exhibiting over four times higher ion conductivities parallel to the layers than perpendicular to the layers. The self-assembled ion pathways allow efficient ion transport in the semi-solid LC state.

Perylene bisimide hydrogels and lyotropic liquid crystals with temperature-responsive color change.

The self-assembly of perylene bisimide (PBI) dyes bearing oligo ethylene glycol (OEG) units in water affords responsive functional nanostructures characterized by their lower critical solution temperature (LCST). Tuning of the LCST is realized by a supramolecular approach that relies on two structurally closely related PBI-OEG molecules. The two PBIs socially co-assemble in water and the resulting nanostructures exhibit a single LCST in between the transition temperatures of the aggregates formed by single components.