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.

Squaraine Appended with Benzodipyrrole for Fluorescent Sensing of Methanol: Exciton Coupling Controls Photophysical Properties.

The photophysical properties of dyes composed of two squaraine chromophores fused with a benzodipyrrole central moiety (BS1 and BS2), were investigated using steady-state absorption, fluorescence, and transient absorption spectroscopy. The dyes exhibit solvent-independent split electronic absorption due to exciton-coupling. Interestingly significant solvent-dependent fluorescence properties were observed. In toluene, they emit from the lowest excited state, while in methanol, they show weak emission in the higher energy region. In the low-temperature glass matrix, emission from the lowest excited state dominates similarly to that in toluene. The transient absorption spectra exhibit similar ground-state bleaching in toluene and methanol, revealing the formation of delocalized excited states by exciton coupling independent of solvent. However, the excited state deactivates rapidly in ultrafast time scale in methanol, likely due to solvent interaction, leading to rapid non-radiative deactivation. The PEG film doped with the exciton-coupled bis-squaraine shows a distinct fluorescence response to methanol vapor.

Controlling the Morphological Features, Aspect Ratio and Emission Patterns of Supramolecular Copolymers by Restricted Dimensional Growth.

One of the bottlenecks associated with supramolecular polymerization of functional π-systems is the spontaneous assembly of monomers leading to one- or two-dimensional (1D or 2D) polymers without control over chain length and optical properties. In the case of supramolecular copolymerization of monomers that are structurally too diverse, preferential self-sorting occurs unless they are closely interacting donor-acceptor pairs. Herein, it is established that the spontaneous 1D polymerization of a phenyleneethynylene (PE) derivative and the 2D polymerization of a Bodipy derivative (BODIPY) can be controlled by copolymerizing them in different ratios, leading to unusual spindle-shaped structures with controlled aspect ratio, as evident by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and confocal laser scanning microscopy (CLSM) studies. For example, when the content of BODIPY is 50 % in the BODIPY-PE mixture, the 1D polymerization of PE is significantly restricted to form elongated spindle-like structures having an aspect ratio of 4-6. The addition of 75 % of BODIPY to PE resulted in circular spindles having an aspect ratio of 1-2.5, thereby completely restricting the 1D polymerization of PE monomers. Moreover, the resultant supramolecular copolymers exhibited morphology and aspect ratio dependent emission features as observed by the time-resolved emission studies.

Photocycloaddition as a Tool for Modulation of the Lower Critical Solution Temperature in a Molecular π-System to Control Transmission of Solar Radiation.

Diels-Alder photocycloaddition, a well-known textbook reaction, has not been explored in materials chemistry. Herein we describe how this classical photochemistry can be used to modulate the lower critical solution temperature (LCST) of a molecular π-system, which can further be exploited for the controlled transmission of solar radiation for the management of indoor heat and light. An amphiphilic anthracene derivative 9-PA-1 exhibited LCST behavior at 27-32 °C with a reversible transition from a transparent to an opaque phase in water (1-5 mM). Irradiation of a toluene solution of 9-PA-1 with 365 nm light resulted in a [4+2] photocycloadduct 9-PA-2, which exhibited a modulated LCST behavior at 25-27 °C, at a concentration as low as 6 µM. The photocycloaddition of 9-PA-1 was significantly retarded in water, making it a stable candidate for the design of sustainable smart windows. We also demonstrated 100 cm2 smart window prototypes (ΔTlum 82 %, ΔTIR 68 %, ΔTsol 73 %) with more than 1000 cycles of stable operation.

Tunable Capacitive Behavior in Metallopolymer-based Electrochromic Thin Film Supercapacitors.

Volumetric capacitance is a more critical performance parameter for rechargeable power supply in lightweight and microelectronic devices as compared to gravimetric capacitance in larger devices. To this end, we report three electrochromic metallopolymer-based electrode materials containing Fe2+ as the coordinating metal ion with high volumetric capacitance and energy densities in a symmetric two-electrode supercapacitor setup. These metallopolymers exhibited volumetric capacitance up to 866.2 F cm-3 at a constant current density of 0.25 A g-1. The volumetric capacitance (poly-Fe-L2: 544.6 F cm-3 > poly-Fe-L1: 313.8 F cm-3 > poly-Fe-L3: 230.8 F cm-3 at 1 A g-1) and energy densities (poly-Fe-L2: 75.5 mWh cm-3 > poly-Fe-L1: 43.6 mWh cm-3 > poly-Fe-L3: 31.2 mWh cm-3) followed the order of the electrical conductivity of the metallopolymers and are among the best values reported for metal-organic systems. The variation in the ligand structure was key toward achieving different electrical conductivities in these metallopolymers with excellent operational stability under continuous cycling. High volumetric capacitances and energy densities combined with tunable electro-optical properties and electrochromic behavior of these metallopolymers are expected to contribute to high performance and compact microenergy storage systems. We envision that the integration of smart functionalities with thin film supercapacitors would warrant the surge of miniaturized on-chip microsupercapacitors integrated in-plane with other microelectronic devices for wearable applications.

Amplified Spontaneous Emission from Zwitterionic Excited-State Intramolecular Proton Transfer.

The unique four-level photocycle characteristics of excited-state intramolecular proton transfer (ESIPT) materials enable population inversion and large spectral separation between absorption and emission through their respective enol and keto forms. This leads to minimal or no self-absorption losses, a favorable feature in acting as an optical gain medium. While conventional ESIPT materials with an enol-keto tautomerism process are widely known, zwitterionic ESIPT materials, particularly those with high photoluminescence, are scarce. Facilitated by the synthesis and characterization of a new family of 2-hydroxyphenyl benzothiazole (HBT) with fluorene substituents, HBT-Fl1 and HBT-Fl2, we herein report the first efficient zwitterionic ESIPT lasing material (HBT-Fl2). The zwitterionic ESIPT HBT-Fl2 not only shows a remarkably low solid-state amplified spontaneous emission (ASE) threshold of 5.3 µJ/cm2 with an ASE peak at 609 nm but also exhibits high ASE photostability. Coupled with its substantially large Stokes shift (≈236 nm ≈10,390 cm-1) and an extremely small overlap of excited-state absorption with ASE emission, comprehensive density functional theory (DFT) and time-dependent DFT studies reveal the zwitterionic characteristics of HBT-Fl2. In opposition to conventional ESIPT with π-delocalized tautomerism as observed in analogue HBT-Fl1 and parent HBT, HBT-Fl2 instead shows charge redistribution in the proton transfer through the fluorene conjugation. This structural motif provides a design tactic in the innovation of new zwitterionic ESIPT materials for efficient light amplification in red and longer-wavelength emission.

Structurally directed thienylenevinylene self-assembly for improved charge carrier mobility: 2D sheets vs. 1D fibers.

High charge carrier mobility is a prerequisite for organic electronics for which molecular arrangement and morphology play a vital role. Herein, we report how the self-assembly of thienylenevinylenes T1 and T2 can achieve morphologically distinct nanostructures with improved charge carrier mobility. Morphological analysis revealed that T1 forms 2D nanosheets that further extend to an array of hierarchical pseudo-1D assemblies, whereas T2 results in 1D nanofibers. Flash photolysis - time resolved microwave conductivity and transient absorption spectroscopy (FP-TRMC and TAS) revealed that 1D fibers of T2 show 1.75 fold higher charge carrier mobility (9.2 × 10-2 cm2 V-1 s-1) when compared to the array of 2D sheets obtained from T1 (5.0 × 10-2 cm2 V-1 s-1). This simple approach can be extended to design self-assembled organic photoconducting materials for optoelectronic applications.

Synthesis, Photophysical and Electrochemical Properties of Bis-Squaraine Dyes Fused on Isomeric Benzodipyrrole Central Units.

Exciton interactions are not only observed in assembled molecules but also in compounds with multiple chromophores referred to as superchromophores. We have developed isomeric bis-squaraine dyes as superchromophores in which two squaraine chromophores are fused onto the isomeric benzodipyrrole skeleton so as to regulate conformations and to reduce distances between two chromophores. The dyes with benzo[1,2-b:3,4-b']dipyrrole and benzo[1,2-b:5,4-b']dipyrrole moieties exhibited split electronic absorption originated from the intramolecular exciton interaction. The intensity of the split absorption bands varies in correlation with the orientation of chromophores. The isomeric dye with benzo[1,2-b:4,5-b']dipyrrole moiety exhibited a near-infrared absorption associated with the resonance throughout two chromophores. Their electrochemical and spectroelectrochemical properties are distinct from those of monomeric dyes owing to electronic interactions between the two chromophores. Thus, the structural isomerism of the central skeleton significantly affects their optical properties as well as their electrochemical properties.

Ligand-Controlled Electrochromic Diversification with Multilayer Coated Metallosupramolecular Polymer Assemblies.

Designing surface-confined molecular systems capable of expressing changes in functional properties as a result of slight variations in chemical structure under the influence of an external stimulus is of contemporary interest. In this context, we have designed three tetraterpyridine ligands with variations in their core architecture (phenyl vs tetraphenylethynyl vs bithiophene) to create spray-coated electrochromic assemblies of iron(II)-based metallosupramolecular polymer network films on transparent conducting oxide substrates. These assemblies exhibited molecular permeability and spectroelectrochemical properties that are in turn dictated by the ligand structure. Electrochromic films with high coloration efficiencies (up to 1050 cm2/C) and superior optical contrast (up to 76%) with a concomitant color-to-color redox transition were readily achieved. These functional switching elements were integrated into sandwich-type electrochromic cells (CE up to 641 cm2/C) that exhibited high contrast ratios of up to 56%, with attractive ON-OFF ratios, fast switching kinetics, and high operational stability. Every measurable spectroelectrochemical property of the films and devices is an associated function of the ligand structure that coordinates the same metal ion to different extents. While exhibiting a ligand-structure induced differential metal coordination leading to porosity and spectroelectrochemical diversification, these assemblies allow the creation of electrochromic patterns and images by a simple spray-coating technique.

Tweaking a BODIPY Spherical Self-Assembly to 2D Supramolecular Polymers Facilitates Excited-State Cascade Energy Transfer.

Excited state properties such as emission, exciton transport, electron transfer, etc., are strongly dependent on the shape, size and molecular arrangement of chromophore based supramolecular architectures. Herein, we demonstrate creation and control of distinct supramolecular energy landscapes for the reversible control of the excited-state emission processes through cascade energy transfer in chromophore assemblies, facilitated by an unprecedented solvent effect. In methylcyclohexane, a tailor-made Y-shaped BODIPY derivative self-assembles to form an unusual spherical architecture of 400-1200 nm size, which exhibits a single emission at 540 nm upon 475 nm excitation through a normal excitation deactivation process. However, in n-decane, the same BODIPY derivative forms two-dimensional supramolecular sheets, exhibiting multiple emission peaks at 540, 610, 650, 725 and 790 nm with 475 nm excitation due to cascade energy transfer. Further control on the morphology and excitation energy transfer is possible with variable solvent composition and ultrasound stimulation, resulting in enhanced near-infrared emission with an overall pseudo Stokes shift of 7105 cm-1 .

Thermochromic Color Switching to Temperature Controlled Volatile Memory and Counter Operations with Metal-Organic Complexes and Hybrid Gels.

Temperature is often not considered as a precision stimulus for artificial chemical systems in contrast to the host-guest interactions related to many natural processes. Similarly, mimicking multi-state volatile memory operations using a single molecular system with temperature as a precision stimulus is highly laborious. Here we demonstrate how a mixture of iron(II) chloride and bipyridine can be used as a reversible color-to-colorless thermochromic switch and logic operators. The generality of the approach was illustrated using CoII and NiII salts that resulted in color-to-color transitions. DMSO gels of these systems, exhibited reversible opaque-transparency switching. More importantly, optically readable multi-state volatile memory with temperature as a precision input has been demonstrated. The stored data is volatile and is lost instantaneously upon withdrawal or change of temperature. Simultaneous read-out at multiple wavelengths results in single-input/multi-output sequential logic operations such as data accumulators (counters) leading to volatile memory states. The present system provides access to thermoresponsive materials wherein temperature can be used as a precision stimulus.

Regulating Back Electron Transfer through Donor and π-Spacer Alterations in Benzothieno[3,2-b]indole-based Dye-sensitized Solar Cells.

Three metal-free organic D-π-A dyes with benzothieno[3,2-b]indole as electron donor, cyanoacrylic acid as both electron acceptor and anchoring group with benzene (BID-1), thiophene (BID-2) and furan (BID-3) as π-spacers were designed and synthesized for application in dye-sensitized solar cells (DSSCs). A planar and electron-rich heterocycle such as benzothieno[3,2-b]indole offers better backbone rigidity and improves charge transport properties in comparison to indolo[3,2-b]indole donor, previously reported from our group. Additionally, we synthesized a benzothieno[3,2-b]indole donor grafted with longer alkyl chains which efficiently prevented the approach of oxidized species in the electrolyte coming closer to semiconductor thereby arresting recombination. A power conversion efficiency of 4.11 % was achieved for dye-sensitized solar cells based on the furan π-spacer benzothieno[3,2-b]indole dye BID-3 in comparison to the corresponding indolo[3,2-b]indole dye (IID-3) having an efficiency of 1.71 %. Detailed interfacial electrical measurements along with theoretical calculations disclosed the mechanism of back electron transfer and improvement in photovoltaic performance with respect to variation in both donor and π-spacer.

Silicon Shadow Mask Technology for Aligning and In Situ Sorting of Semiconducting SWNTs for Sensitivity Enhancement: A Case Study of NO2 Gas Sensor.

Single-walled carbon nanotubes (SWNTs) are incorporated in different device configurations such as chemiresistors and field-effect transistors (FETs) as a sensing element for the fabrication of highly sensitive and specific biochemical sensors. For this purpose, sorting and aligning of semiconducting SWNTs between the electrodes is advantageous. In this work, a silicon shadow mask fabricated using conventional semiconductor processes and silicon bulk micromachining was used to make metal contacts over SWNTs with a minimum feature of 1 µm gap between the electrodes. The developed silicon shadow mask-based metal contact patterning process is cost-effective and free from photoresist (PR) chemical coatings and thermal processing. After a detailed investigation, sodium dodecyl sulfate (SDS), an anionic surfactant, along with ultrasonication process, was found to be effective for the removal of unclamped and metallic SWNTs, resulting in aligned and clamped semiconducting SWNTs between the electrodes. The presence of aligned semiconducting SWNTs was confirmed using atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM), and Raman spectroscopy techniques. The fabricated devices were tested for nitrogen dioxide (NO2) gas sensing as a test case. The sensitivity enhancement of ∼21 to 76% in the 20-80 ppm NO2 concentration range has been observed in the case of aligned semiconducting SWNT devices compared to the random network SWNT-based sensors.

Self-Assembled Extended π-Systems for Sensing and Security Applications.

Molecules and materials derived from self-assembled extended π-systems have strong and reversible optical properties, which can be modulated with external stimuli such as temperature, mechanical stress, ions, the polarity of the medium, and so on. In many cases, absorption and emission responses of self-assembled supramolecular π-systems are manifested several times higher when compared with the individual molecular building blocks. These properties of molecular assemblies encourage scientists to have a deeper understanding of their design to explore them for suitable optoelectronic applications. Therefore, it is important to bring in highly responsive optical features in π-systems, for which it is necessary to modify their structures by varying the conjugation length and by introducing donor-acceptor functional groups. Using noncovalent forces, π-systems can be put together to form assemblies of different shapes and sizes with varied optical band gaps through controlling intermolecular electronic interactions. In addition, using directional forces, it is possible to bring anisotropy to the self-assembled nanostructures, facilitating efficient exciton migration, resulting in the modulation of optical and electron-transport properties. In this Account, we mainly summarize our findings with optically tunable self-assemblies of extended π-systems such as p-phenylenevinylenes (PVs), p-phenyleneethynylenes (PEs), and diketopyrrolopyrroles (DPPs) as different stimuli-responsive platforms to develop sensors and security materials. We start with how PV self-assemblies and their coassemblies with appropriate electron-deficient systems can be used for the sensing of analytes in contact mode or in the vapor phase. For example, whereas the PV having electron-deficient terminal groups has high sensitivity toward trinitrotoluene (TNT) in contact mode, the supercoiled fibers formed by the coassembly of self-sorted stacks of C3-symmetrical PV and C3-symmetrical electron-deficient perylene bisimide are capable of sensing vapors of nitrobenzene and o-toluidine. The power of different functional groups in combination with PVs has been further illustrated by attaching CO2-sensitive tertiary amine moieties to a cyano-substituted PV, which allowed the bimodal detection of CO2 using fluorescence and Raman spectroscopy. Interestingly, the functionalization of PVs with terminal amide groups and chiral alkoxy side chains provided a mechanochromic system that allows self-erasable imaging. Whereas PVs exhibit quenching of fluorescence in most cases during self-assembly, PE derivatives exhibit aggregation-induced emission. This property of PEs has been exploited for the development of stimuli-responsive security materials, especially for currency and documents. For instance, the blue fluorescence of a PE attached to hydrophilic oxyethylene side chains coated on a filter paper upon contact with water changes to cyan emission due to the change in the molecular packing. Interestingly, the molecular packing of a Bodipy-attached PE-based gelator allowed a stress-induced change in the emission behavior, resulting in strong near-infrared (NIR) emission upon the application of mechanical stress or gelation. Finally, the use of DPP-based π-systems for the development of NIR transparent optical filters that block UV-vis light and their security- and forensic-related applications are described. These selected examples of the π-system self-assemblies provide an idea of the current status and future opportunities for scientists interested in this field of self-assembly and soft materials research.

A new pentacyclic pyrylium fluorescent probe that responds to pH imbalance during apoptosis.

Efficient fluorophores with easy synthetic routes and fast responses are of great importance in clinical diagnostics. Herein, we report a new, rigid pentacyclic pyrylium fluorophore, PS-OMe, synthesised in a single step by a modified Vilsmeier-Haack reaction. Insights into the reaction mechanism facilitated a new reaction protocol for the efficient synthesis of PS-OMe which upon demethylation resulted in a "turn-on" pH sensor, PS-OH. This new fluorescent probe has been successfully used to monitor intracellular acidification at physiological pH. From the fluorescence image analysis, we were able to quantify the intracellular dynamic pH change during apoptosis. This new pH probe is a potential chemical tool for screening, drug discovery and dose determination in cancer therapy.

Supramolecular Surface Charge Regulation in Ionic Covalent Organic Nanosheets: Reversible Exfoliation and Controlled Bacterial Growth.

Poor control on the exfoliation of covalent organic frameworks (COFs) remains a disadvantage for their application as two-dimensional nanosheets. An equally important problem is the reversible control at the available surface charges on COFs. Herein, a strategy for the reversible exfoliation, re-stacking, and surface-charge control of a propidium iodide based ionic covalent organic framework, PI-TFP, using cucurbit[7]uril (CB[7]) induced molecular recognition, is reported. The surface charge on PI-TFP facilitates its initial self-exfoliation. However, complexation with CB[7] resulted in re-stacking with concomitant decrease in zeta potential from +28±3.0 to +0.004±0.003 mV. Addition of 1-adamantylamine hydrochloride (AD) facilitates decomplexation of PI-TFP from CB[7], resulting in exfoliation and an increase in zeta potential to +24±3.0 mV. Such control on the exfoliation, re-stacking, and the associated regulation of the surface charge in PI-TFP was exploited for controlling bacterial growth. Thus, the activity of E. coli and S. aureus bacteria obtained with the self-exfoliated PI-TFP could be reversibly controlled by the CB[7]/AD pair.

Bimodal detection of carbon dioxide using fluorescent molecular aggregates.

Cyano-substituted p-phenylenevinylene (R-1) aggregates exhibiting fluorescence and Raman spectroscopic responses towards CO2 are described. The aggregation-induced emission (AIE) as well as the aggregation-enhanced Raman scattering (AERS) of R-1 in aqueous conditions was reduced in the presence of a small amount of CO2, which enabled its easy and fast bimodal detection in different analytical samples.

Supramolecular Gel Phase Controlled [4 + 2] Diels-Alder Photocycloaddition for Electroplex Mediated White Electroluminescence.

Diels-Alder photocycloaddition of 9-phenylethynylanthracene results in multiple [4 + 2] and [4 + 4] cycloaddition products in solution, which can be controlled to form specific products under a restricted environment. We have exploited the gel phase of a 9-phenylethynylanthracence derivative as a confined medium to specifically yield the [4 + 2] cycloadduct in >90% yield. The photocycloadduct ( anti-form) exhibited a blue emission with CIE chromaticity of x = 0.16/ y = 0.16. Construction of an organic light emitting device with the photocycloadduct, using a carbazole-based hole transporting host, resulted in white light emission with a CIE chromaticity of x = 0.33/ y = 0.32. This observation not only highlights the use of gel chemistry to achieve the otherwise difficult to obtain photoproducts but also underlines their potential in optoelectronic device fabrication.

Controlling the Supramolecular Polymerization of Donor-Acceptor π-Systems through Hydrogen Bond Intervention.

Supramolecular polymerization of donor-acceptor type molecules leads to mixed or self-sorted assemblies depending on the donor-acceptor strength and extent of noncovalent interactions between the components. Herein, we discuss how competing hydrogen bonding motifs control the supramolecular polymerization pathway of a two-component molecular π-system of oligo(p-phenylenevinylene) (OPV-B and OPV-P) donors and perylene bisimide (PBI-B and PBI-A) acceptors. It is shown that among the four different binary combinations (M1-M4) studied, the carboxylic acid/pyridine heterosystem (1 : 2 molar ratio) in M4 favors the coassembled donor-acceptor stacks with a distinct morphology, whose aggregation pathways in toluene/THF (v/v : 9/1) is different from that of the individual components. The nanoscopic molecular arrangement of OPV-P driven by PBI-A in M4 was found to influence the bulk properties such as, morphology, thermomechanical stability and electrical conductivity. For example, the G' and G'' values of M4 is an order of the magnitude higher and exhibited a four-probe electrical conductivity (11.93 Scm-1 ) higher than that of its individual components. Thus, hydrogen-bond intervention is a powerful strategy to control the supramolecular polymerization of two-component donor-acceptor π-systems.

Charge Carrier Polarity Modulation in Diketopyrrolopyrrole-Based Low Band Gap Semiconductors by Terminal Functionalization.

Organic semiconductors with variable charge carrier polarity are required for optoelectronic applications. Herein, we report the synthesis of three novel diketopyrrolopyrrole (DPP)-based D-A molecules having three different terminal groups (amide, ester, and dicyano) and study their electronic properties. An increase in electron acceptor strength from amide to dicyano leads to a bathochromic shift in absorption. Photoconductivity and field effect transistor (FET) measurements confirmed that a small increase in acceptor strength can result in a large change in the charge transport properties from p-type to n-type. The molecule with an amide group, DPP-amide, exhibited a moderate p-type mobility (1.3 × 10-2 cm2 V-1 s-1), whereas good n-type mobilities were observed for molecules with an ester moiety, DPP-ester (1.5 × 10-2 cm2 V-1 s-1), and with a dicyano group, DPP-DCV (1 × 10-2 cm2 V-1 s-1). The terminal functional group modification approach presented here is a simple and efficient method to alter the charge carrier polarity of organic semiconductors.