Porous Organic Nanotubes: Chemistry of One-Dimensional Space.

ConspectusOne-dimensional organic nanotubes feature unique properties, such as confined chemical environments and transport channels, which are highly desirable for many applications. Advances in synthetic methods have enabled the creation of different types of organic nanotubes, including supramolecular, hydrogen-bonded, and carbon nanotube analogues. However, challenges associated with chemical and mechanical stability along with difficulties in controlling aspect ratios remain a significant bottleneck. The fascination with structured porous materials has paved the way for the emergence of reticular solids such as metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and organic cages. Reticular materials with tubular morphology promise architectural stability with the additional benefit of permeant porosity. Despite this, the current synthetic approaches to these reticular nanotubes focus more on structural design resulting in less reliable morphological uniformity. This Account, highlights the design motivation behind various classes of organic nanotubes, emphasizing their porous interior space. We explore the strategic assembly of organic nanotubes based on their bonding characteristics, from weak supramolecular to robust covalent interactions. Special attention is given to reticular nanotubes, which have gained prominence over the past two decades due to their distinctive micro and mesoporous structures. We examine the synergy of covalent and noncovalent interactions in constructing assembly of these nanotube structures.This Account furnishes a comprehensive overview of our efforts and advancements in developing porous covalent organic nanotubes (CONTs). We describe a general synthetic approach for creating robust imine-linked nanotubes based on the reticular chemistry principles. The use of spatially oriented tetratopic triptycene-based amine and linear ditopic aldehyde building blocks facilitates one-dimensional nanotube growth. The interplay between directional covalent bonds and solvophobic interactions is crucial for forming uniform, well-defined, and high aspect ratio nanotubes. The nanotubes derive their permeant porosity and thermal and chemical stability from their covalent architecture. We also highlight the adaptability of our synthetic methodology to guide the transformation of one-dimensional nanotubes to toroidal superstructures and two-dimensional thin fabrics. Such morphological transformation can be directed by tuning the reaction time or incorporating additional intermolecular interactions to control the intertwining behavior of individual nanotubes. The cohesion of covalent and noncovalent interactions in the tubular nanostructures manifests superior viscoelastic mechanical properties in the assembled CONT fabrics. We establish a strong correlation between structural framework design and nanostructures by translating reticular synthesis to morphological space and gaining insights into the assembly processes. We anticipate that the present Account will lay the foundation for exploring new designs and chemistry of organic nanotubes for many application platforms.

Metallosupramolecular polymers: current status and future prospects.

Metallo-supramolecular polymers have gained increasing attention and witnessed continuous development as a vibrant new research interest in the domain of soft materials. These nonconventional polymers have found widespread application in materials and biology owing to their well-defined and diversified topologies and the distinct dynamic nature of the metallosupramolecular interactions against various stimuli. Because of the intriguing redox, photonic, electronic, and magnetic properties, these stimuli-responsive supramolecular structures have attracted considerable interest for optoelectronic device fabrication. However, it still remains challenging to develop stimuli responsive systems with offbeat applications. Furthermore, achieving spatiotemporal control remains elusive with thermoresponsive and sono-responsive metallosupramolecular polymers, which encounter the disadvantage of poor precision control. Additionally, controlling the morphology of these soft materials on the mesoscale, both in solution and on substrates, has many challenges. In this review, we discuss the recent developments and future directions for the construction of stimuli responsive metallosupramolecular systems targeting practical applications. Furthermore, we discuss the synthetic methodologies that have been used to regulate the mesoscale morphology of these materials, such as coordination modulation and pseudomorphic replication. Finally, we briefly cover the burgeoning field of programmed synthesis of metallosupramolecular polymers, emphasizing techniques, such as living polymerization and chemical fuel-driven transiently active systems, which we believe will be the major research directions in the future.

Cascade reaction networks within audible sound induced transient domains in a solution.

Spatiotemporal control of chemical cascade reactions within compartmentalized domains is one of the difficult challenges to achieve. To implement such control, scientists have been working on the development of various artificial compartmentalized systems such as liposomes, vesicles, polymersomes, etc. Although a considerable amount of progress has been made in this direction, one still needs to develop alternative strategies for controlling cascade reaction networks within spatiotemporally controlled domains in a solution, which remains a non-trivial issue. Herein, we present the utilization of audible sound induced liquid vibrations for the generation of transient domains in an aqueous medium, which can be used for the control of cascade chemical reactions in a spatiotemporal fashion. This approach gives us access to highly reproducible spatiotemporal chemical gradients and patterns, in situ growth and aggregation of gold nanoparticles at predetermined locations or domains formed in a solution. Our strategy also gives us access to nanoparticle patterned hydrogels and their applications for region specific cell growth.

Transient Self-assembly Processes Operated by Gaseous Fuels under Out-of-Equilibrium Conditions.

Herein we report transient out-of-equilibrium self-assembly of molecules operated by gaseous fuel mixtures. The combination of an active gaseous chemical fuel and an inert gas or compressed air, which assists the degassing of the gaseous fuel from the solution, drives the transient self-assembly process. The gaseous nature of the fuel as well as the exhaust helps in their easy removal and thereby prevents their accumulation within the system and helps in maintaining the efficiency of the transient self-assembly process. The strategy is executed with a rather simple experimental set up and operates at ambient temperatures. Our approach may find use in the development of smart materials suitable for applications such as temporally active gas sensing and sequestration.

Audible sound-controlled spatiotemporal patterns in out-of-equilibrium systems.

Naturally occurring spatiotemporal patterns typically have a predictable pattern design and are reproducible over several cycles. However, the patterns obtained from artificially designed out-of-equilibrium chemical oscillating networks (such as the Belousov-Zhabotinsky reaction for example) are unpredictable and difficult to control spatiotemporally, albeit reproducible over subsequent cycles. Here, we show that it is possible to generate reproducible spatiotemporal patterns in out-of-equilibrium chemical reactions and self-assembling systems in water in the presence of sound waves, which act as a guiding physical stimulus. Audible sound-induced liquid vibrations control the dissolution of atmospheric gases (such as O2 and CO2) in water to generate spatiotemporal chemical patterns in the bulk of the fluid, segregating the solution into spatiotemporal domains having different redox properties or pH values. It further helps us in the organization of transiently formed supramolecular aggregates in a predictable spatiotemporal manner.

Supramolecular Fullerene Tetramers Concocted with Porphyrin Boxes Enable Efficient Charge Separation and Delocalization.

Herein, we report a novel porphyrin/fullerene supramolecular cocrystal using a shape-persistent zinc-metalated porphyrin box (Zn-PB) and C60/C70. An unprecedented arrangement of a tightly packed square-planar core of four C60 or C70 surrounded by six cube-shaped Zn-PBs was observed. This unique packing promotes strong charge transfer (CT) interactions between the two components in the ground state and formation of charge-separated states with very long lifetimes in the excited state and enables unusually high photoconductivity. Quantum chemical calculations show that these features are enabled by delocalized orbitals that promote the CT, on one hand, and that are spatially separated from each other, on the other hand. This work may open a new avenue to design novel electron donor/acceptor architectures for artificial photosynthesis.

Fuel-Driven Transient Crystallization of a Cucurbit[8]uril-Based Host-Guest Complex.

Transient self-assembling systems often suffer from accumulation of chemical wastes that interfere with the formation of pristine self-assembled products in subsequent cycles. Herein, we report the transient crystallization of a cucurbit[8]uril-based host-guest complex, preventing the accumulation of chemical wastes. Base-catalyzed thermal decarboxylation of trichloroacetic acid that chemically fuels the crystallization process dissolves the crystals, and produces volatile chemical wastes that are spontaneously removed from the solution. With such self-clearance process, no significant damping in the formation of the crystals was observed. The morphology and structural integrity of the crystals was also maintained in subsequent cycles. The concept may be further extended to obtain other temporally functional materials, quasicrystals, etc., based on stimuli-responsive guest molecules.

Rational Design and Construction of Hierarchical Superstructures Using Shape-Persistent Organic Cages: Porphyrin Box-Based Metallosupramolecular Assemblies.

We report a new approach to building hierarchical superstructures using a shape-persistent porous organic cage, which acts as a premade secondary building unit, and coordination chemistry. To illustrate the principle, a zinc-metalated porphyrin box (Zn-PB), a corner-truncated cubic porous cage, was connected by suitable dipyridyl terminated bridging ligands to construct PB-based hierarchical superstructures (PSSs). The PSSs were stabilized not only by the coordination bonds between Zn ions and bipyridyl-terminated ligands but also by π-π interactions between the corners of the Zn-PB units. By varying the length of the linker, we identified an optimum range of the linker length for construction of PSSs. The PSSs have large void volumes and an extrinsic surface area compared to the parent PBs, which can be exploited for the selective encapsulation and interior functionalization of the PSSs for various applications, including catalysis. We observed that singlet oxygen induced synthesis of the natural product, juglone, is more efficiently catalyzed by PSS-1 than its constituent component Zn-PB.

Porphyrin Boxes.

In order to fabricate efficient molecular photonic devices, it has been a long-held aspiration for chemists to understand and mimic natural light-harvesting complexes where a rapid and efficient transfer of excitation energy between chlorophyll pigments is observed. Synthetic porphyrins are attractive building blocks in this regard because of their rigid and planar geometry, high thermal and electronic stability, high molar extinction, small and tunable band gap, and tweakable optical as well as redox behavior. Owing to these fascinating properties, various types of porphyrin-based architectures have been reported utilizing both covalent and noncovalent approaches. However, it still remains a challenge to construct chemically robust, well-defined three-dimensional porphyrin cages which can be easily synthesized and yet suitable for useful applications both in solution as well as in solid state. Working on this idea, we recently synthesized box-shaped organic cages, which we called porphyrin boxes, by making use of dynamic covalent chemistry of imine condensation reaction between 4-connecting, square-shaped, tetraformylporphyrin and 3-connecting, triangular-shaped, triamine molecules. Various presynthetic, as well as postsynthetic modifications, can be carried out on porphyrin boxes including a variation of the alkyl chain length in their 3-connecting subunit, chemical functionalization, and metalation of the porphyrin core. This can remarkably tune their inherent properties, e.g., solubility, window size, volume, and polarity of the internal void. The porphyrin boxes can therefore be considered as a significant addition to the family of multiporphyrin-based architectures, and because of their chemical stability and shape persistency, the applications of porphyrin boxes expand beyond the photophysical properties of an artificial light-harvesting complex. Consequently, they have been exploited as porous organic cages, where their gas adsorption properties have been investigated. By incorporating them in a lipid bilayer membrane, an iodide selective synthetic ion channel has also been demonstrated. Further, we have explored electrocatalytic reduction of carbon dioxide using Fe(III) metalated porphyrin boxes. Additionally, the precise size and ease of metalation of porphyrin boxes allowed us to utilize them as premade building blocks for creating coordination-based hierarchical superstructures. Considering these developments, it may be worth combining the photophysical properties of porphyrin with the shape-persistent porous nature of porphyrin boxes to explore other novel applications. This Account summarizes our recent work on porphyrin boxes, starting with their design, structural features, and applications in different fields. We also try to provide scientific insight into the future opportunities that these amazing boxes have in store for exploring the still uncharted challenging domains in the field of supramolecular chemistry in a confined space.

Stepwise control of host-guest interaction using a coordination polymer gel.

Precise control of host-guest interaction as seen in biological processes is difficult to achieve with artificial systems. Herein we have exploited the thermodynamic benefits of a system in equilibrium to achieve controlled stepwise release and capture of cyclodextrin (guest) using a coordination polymer (Mg-CP) as the host and temperature as the stimulus. Since temperature is not a precision stimulus for artificial host-guest interaction, the present system is a distinct prototype that manifests temperature-controlled natural host-guest interaction. The described coordination polymeric host system, when incorporated into a hydrogel matrix, provides a microenvironment that facilitates the stepwise release of α-CD in response to temperature variation within a quasi-solid state. The work demonstrated here may pave the way towards thermally controlled delivery and monitoring of otherwise spectroscopically silent molecules such as cyclodextrins.

Creation of "Rose Petal" and "Lotus Leaf" Effects on Alumina by Surface Functionalization and Metal-Ion Coordination.

Functional differences between superhydrophobic surfaces, such as lotus leaf and rose petals, are due to the subtle architectural features created by nature. Mimicry of these surfaces with synthetic molecules continues to be fascinating as well as challenging. Herein, we demonstrate how inherently hydrophilic alumina surface can be modified to give two distinct superhydrophobic behaviors. Functionalization of alumina with an organic ligand resulted in a rose-petal-like surface (water pinning) with a contact angle of 145° and a high contact angle hysteresis (±69°). Subsequent interaction of the ligand with Zn2+ resulted in a lotus-leaf-like surface with water rolling behavior owing to high contact angle (165°) and low-contact-angle-hysteresis (±2°). In both cases, coating of an aromatic bis-aldehyde with alkoxy chain substituents was necessary to emulate the nanowaxy cuticular feature of natural superhydrophobic materials.

A π-gel scaffold for assembling fullerene to photoconducting supramolecular rods.

Nonequilibrium self-assembly of molecules holds a huge prospect as a tool for obtaining new-generation materials for future applications. Crystallization of neutral molecules within a supramolecular gel matrix is one example in which two nonequilibrium processes occur orthogonal to each other. On the other hand, electronically interacting donor-acceptor two-component systems are expected to form phase-miscible hybrid systems. Contrary to the expectation, we report the behavior of a π-gel, derived from oligo(p-phenylenevinylene), OPVA, as a scaffold for the phase separation and crystallization of fullerene (C60) to supramolecular rods with increased transient photoconductivity (φÆ©µmax = 2.4 × 10-4 cm2 V-1 s-1). The C60 supramolecular rods in the π-gel medium exhibited high photocurrent in comparison to C60 loaded in a non-π-gel medium. This finding provides an opportunity for large-scale preparation of micrometer-sized photoconducting rods of fullerenes for device application.

A slippery molecular assembly allows water as a self-erasable security marker.

Protection of currency and valuable documents from counterfeit continues to be a challenge. While there are many embedded security features available for document safety, they are not immune to forgery. Fluorescence is a sensitive property, which responds to external stimuli such as solvent polarity, temperature or mechanical stress, however practical use in security applications is hampered due to several reasons. Therefore, a simple and specific stimuli responsive security feature that is difficult to duplicate is of great demand. Herein we report the design of a fluorescent molecular assembly on which water behaves as a self-erasable security marker for checking the authenticity of documents at point of care. The underlying principle involves the disciplined self-assembly of a tailor-made fluorescent molecule, which initially form a weak blue fluorescence (λem = 425 nm, Φf = 0.13) and changes to cyan emission (λem = 488 nm,Φf = 0.18) in contact with water due to a reversible molecular slipping motion. This simple chemical tool, based on the principles of molecular self-assembly and fluorescence modulation, allows creation of security labels and optically masked barcodes for multiple documents authentication.

Light driven mesoscale assembly of a coordination polymeric gelator into flowers and stars with distinct properties.

Control over the self-assembly process of porous organic-inorganic hybrids often leads to unprecedented polymorphism and properties. Herein we demonstrate how light can be a powerful tool to intervene in the kinetically controlled mesoscale self-assembly of a coordination polymeric gelator. Ultraviolet light induced coordination modulation via photoisomerisation of an azobenzene based dicarboxylate linker followed by aggregation mediated crystal growth resulted in two distinct morphological forms (flowers and stars), which show subtle differences in their physical properties.

Supramolecular gels and functional materials research in India.

Supramolecular gels are a class of soft materials made up of small molecules held together through non-covalent interactions. They have reversible properties and a wide range of applications. Chromophore-based gels are of particular interest due to their inherent electronic properties such as emission and charge transport useful for organic electronic device fabrication. Significant contributions have been made by Indian researchers in this area, which are highlighted in this mini review.