Enzymatic Reaction-Coupled, Cooperative Supramolecular Polymerization.

Nature employs sophisticated mechanisms to precisely regulate self-assembly and functions within biological systems, exemplified by the formation of cytoskeletal filaments. Various enzymatic reactions and auxiliary proteins couple with the self-assembly process, meticulously regulating the length and functions of resulting macromolecular structures. In this context, we present a bioinspired, reaction-coupled approach for the controlled supramolecular polymerization in synthetic systems. To achieve this, we employ an enzymatic reaction that interfaces with the adenosine triphosphate (ATP)-templated supramolecular polymerization of naphthalene diimide monomers (NSG). Notably, the enzymatic production of ATP (template) plays a pivotal role in facilitating reaction-controlled, cooperative growth of the NSG monomers. This growth process, in turn, provides positive feedback to the enzymatic production of ATP, creating an ideal reaction-coupled assembly process. The success of this approach is further evident in the living-growth characteristic observed during seeding experiments, marking this method as the pioneering instance where reaction-coupled self-assembly precisely controls the growth kinetics and structural aspects of supramolecular polymers in a predictive manner, akin to biological systems.

Controlled Supramolecular Polymerization via Bioinspired, Liquid-Liquid Phase Separation of Monomers.

Dynamic supramolecular assemblies, driven by noncovalent interactions, pervade the biological realm. In the synthetic domain, their counterparts, supramolecular polymers, endowed with remarkable self-repair and adaptive traits, are often realized through bioinspired designs. Recently, controlled supramolecular polymerization strategies have emerged, drawing inspiration from protein self-assembly. A burgeoning area of research involves mimicking the liquid-liquid phase separation (LLPS) observed in proteins to create coacervate droplets and recognizing their significance in cellular organization and diverse functions. Herein, we introduce a novel perspective on synthetic coacervates, extending beyond their established role in synthetic biology as dynamic, membraneless phases to enable structural control in synthetic supramolecular polymers. Drawing parallels with the cooperative growth of amyloid fibrils through LLPS, we present metastable coacervate droplets as dormant monomer phases for controlled supramolecular polymerization. This is achieved via a π-conjugated monomer design that combines structural characteristics for both coacervation through its terminal ionic groups and one-dimensional growth via a π-conjugated core. This design leads to a unique temporal LLPS, resulting in a metastable coacervate phase, which subsequently undergoes one-dimensional growth via nucleation within the droplets. In-depth spectroscopic and microscopic characterization provides insights into the temporal evolution of disordered and ordered phases. Furthermore, to modulate the kinetics of liquid-to-solid transformation and to achieve precise control over the structural characteristics of the resulting supramolecular polymers, we invoke seeding in the droplets, showcasing living growth characteristics. Our work thus opens up new avenues in the exciting field of supramolecular polymerization, offering general design principles and controlled synthesis of precision self-assembled structures in confined environments.

Revisiting organic charge-transfer cocrystals for wide-range tunable, ambient phosphorescence.

Simple and efficient designs that enable a wide range of phosphorescence emission in organic materials have ignited scientific interest across diverse fields. One particularly promising approach is the cocrystallization strategy, where organic cocrystals are ingeniously formed through relatively weaker and dynamic non-covalent interactions. In our present study, we push the boundaries further by extending this cocrystal strategy to incorporate donor-acceptor components, stabilized by various halogen bonding interactions. This non-covalent complexation triggers ambient, charge-transfer phosphorescence (3CT), which can be precisely tuned across a broad spectrum by a modular selection of components with distinct electronic characteristics. At the core of our investigation lies the electron-deficient phosphor, pyromellitic diimide, which, upon complexation with different donors based on their electron-donating strength, manifests a striking array of phosphorescence emission from CT triplet states, spanning from green to yellow to reddish orange accompanied by noteworthy quantum yields. Through a systematic exploration of the electronic properties using spectroscopic studies and molecular organization through single-crystal X-ray diffraction, we decisively establish the molecular origin of the observed phosphorescence. Notably, our work presents, for the first time, an elegant demonstration of tunable 3CT phosphorescence emission in intermolecular donor-acceptor systems, highlighting their immense significance in the quest for efficient organic phosphors.

Controlled Noncovalent Synthesis of Secondary Supramolecular Polymers.

Dynamic supramolecular polymers, with their functional similarities to classical covalent polymers and their adaptive and self-repairing nature reminiscent of biological assemblies, have emerged as highly promising systems for the design of smart soft materials. Recent advancements in mechanistic investigations and novel synthetic strategies, such as living supramolecular polymerization, have significantly enhanced our ability to control the primary structure of these supramolecular polymers. However, realizing their full functional potential requires expanding their topological diversity in a manner akin to classical polymers as well as achieving precise molecular organization at higher hierarchical levels of self-assembly. In this paper, we present a remarkable advancement in this field, introducing an unprecedented and controlled synthesis of secondary supramolecular polymers. Our innovative strategy combines chirality-controlled surface-catalyzed secondary nucleation and a bioinspired peptide design, effectively stabilizing higher-order assembly. Furthermore, by harnessing this stereoselective nucleation process, we demonstrate the successful synthesis of racemic supramolecular polymers featuring parallelly stacked conglomerate microstructures─a previously unreported topology in synthetic self-assembled systems. Additionally, we elucidate that the extent of secondary supramolecular polymers can be regulated by modulating the enantiomeric excess of the chiral monomers. Consequently, our study unveils new topologies that exhibit enhanced higher-order structural complexity in the realm of supramolecular polymers.

Chiroptical Amplification of Induced Circularly Polarized Luminescence in Nucleotide-Templated Supramolecular Polymer.

Efficient circularly polarized luminescence (CPL) from purely organic molecules holds great promise for applications in displays, sensing, and bioimaging. However, achieving high dissymmetry values (glum ) from organic chromophores remains a significant challenge. Herein, we present a bioinspired approach using adenosine triphosphate (ATP)-triggered supramolecular polymerization of a naphthalene diimide-derived monomer (ANSG) to induce CPL with a remarkable glum value of 1.1×10-2 . The ANSG molecules undergo a templated, chiral self-assembly through a cooperative growth mechanism in the presence of ATP, resulting in scrolled nanotubes with aggregation-induced enhanced emission (AIEE) and induced CPL. Furthermore, we demonstrate the concept of chiroptical amplification of induced CPL by efficiently amplifying asymmetry using a mixture of chiral ATP and achiral pyrophosphate. This innovative approach opens numerous opportunities in the emerging field of circularly polarized luminescence.

Emulating Ebbinghaus forgetting behavior in a neuromorphic device based on 1D supramolecular nanofibres.

Mimicking synaptic functions in hardware devices is a crucial step in realizing brain-like computing beyond the von Neumann architecture. 1D nanomaterials with spatial extensions of a few µm, similar to biological neurons, gain significance given the ease of electrical transport as well as directionality. Herein, we report a two-terminal optically active device based on 1D supramolecular nanofibres consisting of CS (coronene tetracarboxylate) and DMV (dimethyl viologen) forming alternating D-A (donor-acceptor) pairs, emulating synaptic functions such as the STP (short-term potentiation), LTP (long-term potentiation), PPF (paired-pulse facilitation), STDP (spike-time dependent plasticity) and learning-relearning behaviors. In addition, an extensive study on the less explored Ebbinghaus forgetting curve has been carried out. The supramolecular nanofibres being light sensitive, the potential of the device as a visual system is demonstrated using a 3 × 3 pixel array.

Fabrication of High-Performance Visible-Blind Ultraviolet Photodetectors Using Electro-ionic Conducting Supramolecular Nanofibers.

The detection of ultraviolet (UV) light is vital for various applications, such as chemical-biological analysis, communications, astronomical studies, and also for its adverse effects on human health. Organic UV photodetectors are gaining much attention in this scenario because they possess properties such as high spectral selectivity and mechanical flexibility. However, the achieved performance parameters are much more inferior than the inorganic counterparts because of the lower mobility of charge carriers in organic systems. Here, we report the fabrication of a high-performance visible-blind UV photodetector, using 1D supramolecular nanofibers. The nanofibers are visibly inactive and exhibit highly responsive behavior mainly for UV wavelengths (275-375 nm), the highest response being at ∼275 nm. The fabricated photodetectors demonstrate desired features, such as high responsivity and detectivity, high selectivity, low power consumption, and good mechanical flexibility, because of their unique electro-ionic behavior and 1D structure. The device performance is shown to be improved by several orders through the tweaking of both electronic and ionic conduction pathways while optimizing the electrode material, external humidity, applied voltage bias, and by introducing additional ions. We have achieved optimum responsivity and detectivity values of around 6265 A W-1 and 1.54 × 1014 Jones, respectively, which stand out compared with the previous organic UV photodetector reports. The present nanofiber system has great potential for integration in future generations of electronic gadgets.

Room temperature charge-transfer phosphorescence from organic donor-acceptor Co-crystals.

Engineering the electronic excited state manifolds of organic molecules can give rise to various functional outcomes, including ambient triplet harvesting, that has received prodigious attention in the recent past. Herein, we introduce a modular, non-covalent approach to bias the entire excited state landscape of an organic molecule using tunable 'through-space charge-transfer' interactions with appropriate donors. Although charge-transfer (CT) donor-acceptor complexes have been extensively explored as functional and supramolecular motifs in the realm of soft organic materials, they could not imprint their potentiality in the field of luminescent materials, and it still remains as a challenge. Thus, in the present study, we investigate the modulation of the excited state emission characteristics of a simple pyromellitic diimide derivative on complexation with appropriate donor molecules of varying electronic characteristics to demonstrate the selective harvesting of emission from its locally excited (LE) and CT singlet and triplet states. Remarkably, co-crystallization of the pyromellitic diimide with heavy-atom substituted and electron-rich aromatic donors leads to an unprecedented ambient CT phosphorescence with impressive efficiency and notable lifetime. Further, gradual minimizing of the electron-donating strength of the donors from 1,4-diiodo-2,3,5,6-tetramethylbenzene (or 1,2-diiodo-3,4,5,6-tetramethylbenzene) to 1,2-diiodo-4,5-dimethylbenzene and 1-bromo-4-iodobenzene modulates the source of ambient phosphorescence emission from the 3CT excited state to 3LE excited state. Through comprehensive spectroscopic, theoretical studies, and single-crystal analyses, we elucidate the unparalleled role of intermolecular donor-acceptor interactions to toggle between the emissive excited states and stabilize the triplet excitons. We envisage that the present study will be able to provide new and innovative dimensions to the existing molecular designs employed for triplet harvesting.

Anion-π-Induced Room Temperature Phosphorescence from Emissive Charge-Transfer States.

The burgeoning noncovalent interactions between π-acidic aromatic surfaces and anions have been recently shown to have unique functional relevance in anion transport, ion sensing, and organocatalysis. Despite its potential to instigate charge-transfer (CT) states, modulation of the emission features by toggling between the excited states using anion-π interactions is not yet explored. On the other hand, excited states with CT characteristics play an important role in the ambient triplet harvesting of organic chromophores. In this context, herein we propose an anion-π-based molecular design for the introduction of emissive singlet and triplet CT excited states, thereby expanding the functional scope of these weak supramolecular interactions. In the present study, we investigate the anion-π-induced emission from the singlet (1CT) and triplet (3CT) CT states of a dibromo dicationic pyromellitic diimide derivative. Remarkably, we accomplish dual room temperature phosphorescence emission from the anion-π-mediated 3CT state along with the locally excited triplet state (3LE) in solution phase using an organic-inorganic supramolecular scaffolding strategy. Comprehensive steady-state and time-resolved spectroscopy along with theoretical calculations provide detailed insights into the excited-state manifolds of phosphor. We envisage that the present study will expedite new molecular designs based on weak intermolecular interactions for the excited-state engineering of organic chromophores to facilitate ambient triplet harvesting and CT emission.

Secondary Nucleation-Triggered Physical Cross-Links and Tunable Stiffness in Seeded Supramolecular Hydrogels.

Mechanistic understanding and the control of molecular self-assembly at all hierarchical levels remain grand challenges in supramolecular chemistry. Functional realization of dynamic supramolecular materials especially requires programmed assembly at higher levels of molecular organization. Herein, we report an unprecedented molecular control on the fibrous network topology of supramolecular hydrogels and their resulting macroscopic properties by biasing assembly pathways of higher-order structures. The surface-catalyzed secondary nucleation process, a well-known mechanism in amyloid fibrilization and chiral crystallization of small molecules, is introduced as a non-covalent strategy to induce physical cross-links and bundling of supramolecular fibers, which influences the microstructure of gel networks and subsequent mechanical properties of hydrogels. In addition, seed-induced instantaneous gelation is realized in the kinetically controlled self-assembled system under this study, and more importantly, the extent of secondary nucleation events and network topology is manipulated by the concentration of seeds.

Chiral Arylene Diimide Phosphors: Circularly Polarized Ambient Phosphorescence from Bischromophoric Pyromellitic Diimides.

Chiral organic phosphors with circularly polarized room-temperature phosphorescence (CPP) provide new prospects to the realm of circularly polarized luminescence (CPL) materials, owing to the long-lived triplet states and persistent emission. Although several molecular designs show efficient room-temperature phosphorescence (RTP), realization of ambient organic CPP remains a formidable challenge. Herein, we introduce a chiral bischromophoric phosphor design to realize ambient CPP emission by appending molecular phosphors to a chiral diaminocyclohexane core. Thus, solution-processable polymer films of the trans-1,2-diaminocyclohexane (DAC) chiral cores with heavy-atom substituted pyromellitic diimide phosphors, exhibits one of the most efficient exclusive CPP emissions with high phosphorescence quantum yield (≈18 % in air and ≈46 % under vacuum) and significant luminescence dissymmetry factor (|glum |≈4.0×10-3 ).

Stereoselective Primary and Secondary Nucleation Events in Multicomponent Seeded Supramolecular Polymerization.

Bioinspired, kinetically controlled seeded growth has been recently shown to provide length, dispersity, and sequence control on the primary structure of dynamic supramolecular polymers. However, command over the molecular organization at all hierarchical levels for the modulation of higher order structures of supramolecular polymers remains a formidable task. In this context, a surface-catalyzed secondary nucleation process, which plays an important role in the autocatalytic generation of amyloid fibrils and also during the chiral crystallization of small monomers, offers exciting possibilities for topology control in synthetic macromolecular systems by introducing secondary growth pathways compared to the usual primary nucleation-elongation process. However, mechanistic insights into the molecular determinants and driving forces for the secondary nucleation event in synthetic systems are not yet realized. Herein, we attempt to fill this dearth by showing an unprecedented molecular chirality control on the primary and secondary nucleation events in seed-induced supramolecular polymerization. Comprehensive kinetic experiments using in situ spectroscopic probing of the temporal changes of the monomer organization during the growth process provide a unique study to characterize the primary and secondary nucleation events in a supramolecular polymerization process. Kinetic analyses along with various microscopic studies further reveal the remarkable effect of stereoselective nucleation and seeding events on the (micro)structural aspects of the resulting multicomponent supramolecular polymers.

Tricomponent Supramolecular Multiblock Copolymers with Tunable Composition via Sequential Seeded Growth.

Synthesis of supramolecular block co-polymers (BCP) with small monomers and predictive sequence requires elegant molecular design and synthetic strategies. Herein we report the unparalleled synthesis of tri-component supramolecular BCPs with tunable microstructure by a kinetically controlled sequential seeded supramolecular polymerization of fluorescent π-conjugated monomers. Core-substituted naphthalene diimide (cNDI) derivatives with different core substitutions and appended with ß-sheet forming peptide side chains provide perfect monomer design with spectral complementarity, pathway complexity and minimal structural mismatch to synthesize and characterize the multi-component BCPs. The distinct fluorescent nature of various cNDI monomers aids the spectroscopic probing of the seeded growth process and the microscopic visualization of resultant supramolecular BCPs using Structured Illumination Microscopy (SIM). Kinetically controlled sequential seeded supramolecular polymerization presented here is reminiscent of the multi-step synthesis of covalent BCPs via living chain polymerization. These findings provide a promising platform for constructing unique functional organic heterostructures for various optoelectronic and catalytic applications.

Light-Harvesting Supramolecular Phosphors: Highly Efficient Room Temperature Phosphorescence in Solution and Hydrogels.

Solution phase room-temperature phosphorescence (RTP) from organic phosphors is seldom realized. Herein we report one of the highest quantum yield solution state RTP (ca. 41.8 %) in water, from a structurally simple phthalimide phosphor, by employing an organic-inorganic supramolecular scaffolding strategy. We further use these supramolecular hybrid phosphors as a light-harvesting scaffold to achieve delayed fluorescence from orthogonally anchored Sulforhodamine acceptor dyes via an efficient triplet to singlet Förster resonance energy transfer (TS-FRET), which is rarely achieved in solution. Electrostatic cross-linking of the inorganic scaffold at higher concentrations further facilitates the formation of self-standing hydrogels with efficient RTP and energy-transfer mediated long-lived fluorescence.

Kinetically controlled synthesis of supramolecular block copolymers with narrow dispersity and tunable block lengths.

Synthesis of supramolecular block copolymers (BCPs) from small monomers has been recently attempted. However, the lack of dispersity and length control of the blocky segments limits its functional outcome. Herein we demonstrate the synthesis of well-defined supramolecular BCPs with tunable block lengths by varying the monomer to seed ratio in a kinetically controlled seeded supramolecular polymerization process. Structured Illumination microscopy (SIM) and spectroscopic analyses provide structural characterization of these supramolecular BCPs, which offers various possibilities as axial organic heterostructures.

Ambient Room Temperature Phosphorescence and Thermally Activated Delayed Fluorescence from a Core-Substituted Pyromellitic Diimide Derivative.

Triplet harvesting under ambient conditions plays a crucial role in improving the luminescence efficiency of purely organic molecular systems. This requires elegant molecular designs that can harvest triplets either via room temperature phosphorescence (RTP) or by thermally activated delayed fluorescence (TADF). In this context, here we report a donor core-substituted pyromellitic diimide (acceptor) derivative as an efficient charge-transfer molecular design from the arylene diimide family as a triplet emitter. Solution-processed thin films of carbazole-substituted CzPhPmDI display both RTP- and TADF-mediated twin emission with a long lifetime and high efficiency under ambient conditions. The present study not only sheds light on the fundamental photophysical process involved in the triplet harvesting of donor-acceptor organic systems, but also opens new avenues in exploring an arylene diimide class of molecules as potential organic light-emitting materials.

Arylene Diimide Phosphors: Aggregation Modulated Twin Room Temperature Phosphorescence from Pyromellitic Diimides.

Arylene diimide derived ambient organic phosphors are seldom reported despite their potential structural characteristics to facilitate the triplet harvesting. In this context, highly efficient room temperature phosphorescence (RTP) from simple, heavy-atom substituted pyromellitic diimide derivatives in amorphous matrix and crystalline state is reported here. Multiple intermolecular halogen bonding interactions among these phosphors, such as halogen-carbonyl and halogen-π resulted in the modulation of phosphorescence, cyan emission from monomeric state and orange-red emission from its aggregated state, to yield twin RTP emission. Remarkably, the air-stable phosphorescence presented here own one of the highest quantum yield (≈48 %) among various organics in orange-red emissive region.

ATP-Driven Synthetic Supramolecular Assemblies: From ATP as a Template to Fuel.

Adenosine triphosphate (ATP) is a molecular unit of energy that drives various processes in the cellular environment. In this Minireview, we discuss the potential of physical and chemical properties of ATP for the development of bio-inspired, synthetic ATP-induced supramolecular systems with dynamic, stimuli-responsive and active assembly characteristics. Molecular design rules for ATP-induced assemblies with various architectures and their stimuli-responsive structural and functional response are categorized. Special attention is given to the immense potential of ATP-fuelled designs in the nascent field of transient/non-equilibrium supramolecular polymerization for the synthesis of lifelike temporally programmable soft materials. Finally, the existing dearth and fate of ATP-driven systems for future challenges are discussed.

Active Bicomponent Nanoparticle Assembly with Temporal, Microstructural, and Functional Control.

Transient supramolecular self-assembly has evolved as a tool to create temporally programmable smart materials. Yet, so far single-component self-assembly has been mostly explored. In contrast, multicomponent self-assembly provides an opportunity to create unique nanostructures exhibiting complex functional outcomes, newer and different than individual components. Even two-component can result in multiple organizations, such as self-sorted domains or co-assembled heterostructures, can occur, thus making it highly complex to predict and reversibly modulate these microstructures. In this study, we attempted to create active bicomponent nanoparticle assemblies of orthogonally pH-responsive-group-functionalized gold and cadmium selenide nanoparticles with temporal microstructural control on their composition (self-sorted or co-assembly) in order to harvest their emergent transient photocatalytic activity by coupling to temporal changes in pH. Moving towards multicomponent systems can deliver next level control in terms of structural and functional outcomes of supramolecular systems.

Transient dormant monomer states for supramolecular polymers with low dispersity.

Temporally controlled cooperative and living supramolecular polymerization by the buffered release of monomers has been recently introduced as an important concept towards obtaining monodisperse and multicomponent self-assembled materials. In synthetic, dynamic supramolecular polymers, this requires efficient design strategies for the dormant, inactive states of the monomers to kinetically retard the otherwise spontaneous nucleation process. However, a generalized design principle for the dormant monomer states to expand the scope of precision supramolecular polymers has not been established yet, due to the enormous differences in the mechanism, energetic parameters of self-assembly and monomer exchange dynamics of the diverse class of supramolecular polymers. Here we report the concept of transient dormant states of monomers generated by redox reactions as a predictive general design to achieve monodisperse supramolecular polymers of electronically active, chromophoric or donor-acceptor, monomers. The concept has been demonstrated with charge-transfer supramolecular polymers with an alternating donor-acceptor sequence.