Large and long-term photon energy storage in diazetidines [2+2] photocycloaddition.

We report a series of -functionalized phenylbenzoxazoles that offer remarkable energy storage, exceeding 300 J g, for the first time among intermolecular cycloaddition-based molecular solar thermal energy storage systems. The [2 + 2] photocycloaddition of phenylbenzoxazoles generates diazetidine cycloadducts that store energy for up to 23 years in the solid state and release energy upon triggered cycloreversion. The solid-state phase transition contributes to increasing overall energy storage densities, and the dearomative cycloaddition process is revealed to be critical for maximizing the intrinsic energy storage capacities.

Light-regulated morphology control in supramolecular polymers.

Stimuli-responsive materials have gained significant recent interest owing to their versatility and wide applications in fields ranging from materials science to biology. In the majority of examples, external stimuli, including light, act as a remote source of energy to depolymerize/deconstruct certain nanostructures or provide energy for exploring their functional features. However, there is little emphasis on the creation and precise control of these materials.

Supramolecular Organic Ferroelectric Materials from Donor-Acceptor Systems.

Organic ferroelectric (FE) materials, though known for more than a century, are yet to reach close to the benchmark of inorganic or hybrid materials in terms of the magnitude of polarization. Amongst the different classes of organic systems, donor (D)-acceptor (A) charge-transfer (CT) complexes are recognized as promising for ferroelectricity owing to their neutral-to-ionic phase transition at low temperature. This review presents an overview of different supramolecular D-A systems that have been explored for FE phase transitions.

Hierarchical assembly of foldable polymers and applications in organic optoelectronics and antibacterial or antiviral materials.

Aggregation of amphiphilic polymers in block-selective solvents produces different nanostructures, which have been studied extensively for wide-ranging applications. Nevertheless, such immiscibility-driven aggregation does not endow them with the desired structural precision, predictability or surface functional group exposure, which significantly impact their functional applications. More recently, biomimetic folded structures of synthetic macromolecules (mostly oligomers) have come to the fore, but such studies have been limited to probe the secondary structures.

Azoheteroarene and Diazocine Molecular Photoswitches: Self-Assembly, Responsive Materials and Photopharmacology.

Aromatic units tethered with an azo (-N=N-) functionality comprise a unique class of compounds, known as molecular photoswitches, exhibiting a reversible transformation between their E- and Z-isomers in response to photo-irradiation. Photoswitches have been explored extensively in the recent past to prepare dynamic self-assembled materials, optoelectronic devices, responsive biomaterials, and more. Most of such materials involve azobenzenes as the molecular photoswitch and to date, SciFinder lists more than 7000 articles and 1000 patents.

A Hierarchical (Macro)molecular Assembly Assisted by Donor-Acceptor Charge-Transfer Interactions Exhibiting Room-Temperature Ferroelectricity.

This communication reveals co-assembly of an electron-deficient naphthalene-diimide (NDI)-appended polyurethane (P1) and electron-rich pyrene (Py), forming an organogel with prominent room-temperature ferroelectricity. In a non-polar medium, intra-chain hydrogen-bonding among the urethane groups of P1 produces a folded structure with an array of the NDIs in the periphery, which intercalate Py by charge-transfer (CT)-interaction. Such CT-complexation enables slow crystallization of the peripheral hydrocarbons, causing gelation with nanotubular morphology, in which the wall consists of the alternating NDI-Py stack.

Stable room temperature ferroelectricity in hydrogen-bonded supramolecular assemblies of ambipolar π-systems.

This article reports H-bonding driven supramolecular polymerization of naphthalimide (A)-thiophene (D)-naphthalimide (A) (AD A, = 1-4) conjugated ambipolar π-systems and its remarkable impact on room temperature ferroelectricity. Electrochemical studies confirm the ambipolar nature of these AD A molecules with the HOMO-LUMO gap varying between 2.05 and 2.

Control over Multiple Nano- and Secondary Structures in Peptide Self-Assembly.

Herein, we report the rich morphological and conformational versatility of a biologically active peptide (PEP-1), which follows diverse self-assembly pathways to form up to six distinct nanostructures and up to four different secondary structures through subtle modulation in pH, concentration and temperature. PEP-1 forms twisted β-sheet secondary structures and nanofibers at pH 7.4, which transform into fractal-like structures with strong β-sheet conformations at pH 13.

Phototriggered Supramolecular Assembly.

Most of the supramolecular structures lack accuracy at the macroscopic scale because of their spontaneous uncontrolled self-assembly. Although significant progress has been made in understanding the pros and cons of various directional noncovalent interactions and their specific molecular recognition ability, it is only in the recent past that the focus has been shifted toward controlling the dimension, dispersity, and other macroscopic properties of supramolecular assemblies. In this context, recent examples encompass various external stimuli to gain the structural precision in supramolecular assembly, among which light-triggered supramolecular assembly has gained significant interest as it is reagent free and endows the possibility of the controlled synthesis of supramolecular assemblies via manipulation of the light energy, irradiation time, or spatial control.

Ultrathin Two Dimensional (2D) Supramolecular Assembly and Anisotropic Conductivity of an Amphiphilic Naphthalene-Diimide.

Two-dimensional (2D)-supramolecular assemblies of π-conjugated chromophores are relatively less common compared to a large number of recent examples on their low dimensional (0D or 1D) assemblies or 3D architectures. This article reports a rational design for the 2D supramolecular assembly of an amphiphilic core-substituted naphthalene-diimide derivative (cNDI-1). The building block contains a naphthalene-diimide (NDI) chromophore, symmetrically substituted with two dodecyl chains from the aromatic core while the imide positions are functionalized with two hydrophilic wedges containing oligo-oxyethylene chains.

Circularly Polarized Luminescence from Chiral Supramolecular Polymer and Seeding Effect.

H-bonding driven J-type aggregation and cooperative supramolecular polymerization of a sulfur-substituted chiral naphthalene-diimide (NDI)-derivative (S,S)-NDI-2 in decane leads to remarkable enhancement of fluorescence quantum yield (43.3 % from 0.5 % in the monomeric state) and intense CPL signal in the aggregated state with a high luminescence dissymmetry factor (g ) of 4.