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

Excitation energy migration in oligo(p-phenylenevinylene) based organogels: structure-property relationship and FRET efficiency

Excitation energy migration (EM) and assisted energy transfer (ET) properties of a few oligo(p-phenylenevinylene) (OPV) based organogelators with different end functional groups have been studied using picosecond time-resolved emission spectroscopy (TRES). EM was found to be more efficient in OPV gelators with small end functional groups (OPV3-4) when compared to that of the gelators with bulky end groups (OPV1-2) in the gel state. TRES studies at elevated temperature and in chloroform solution highlight the role of the self-assembled scaffolds in assisting the EM and ET processes. Increase in temperature and solvent polarity leads to the aggregate breaking and hence adversely affects the EM and ET efficiencies. The effect of EM efficiency on the fluorescence resonance energy transfer (FRET) properties of the OPV gels was studied by using OPV1 and OPV3 as the donors and OPV5 as the acceptor. Better transfer of excitation energy was observed in the donor system (OPV3) having higher EM efficiency even at very low concentration (3.1 mol%) of the acceptor molecules, whereas ET efficiency was lower in the donor system (OPV1) with low EM efficiency

Morphology control in metallosupramolecular assemblies through solvent-induced steric demand

Controlling the supramolecular self-assembly of pi-conjugated systems into defined morphologies is a prerequisite for the preparation of functional materials. In recent years, the development of sophisticated sample preparation protocols and modulation of various experimental conditions (solvent, concentration, temperature,etc.) have enabled precise control over aggregation pathways of different types of monomer units. A common method to achieve pathway control consists in the combination of two miscible solvents in defined proportions - a "poor" and "good" solvent. However, the role of solvents of opposed polarity in the self-assembly of a given building block still remains an open question. Herein, we unravel the effect of aggregation-inducing solvent systems of opposed polarity (aqueousvs.non-polar media) on the supramolecular assembly of a new bolaamphiphilic Pt(ii) complex. A number of experimental methods show a comparable molecular packing in both media driven by a synergy of solvophobic, aromatic and weak hydrogen-bonding interactions. However, morphological analysis of the respective aggregates in aqueous and non-polar media reveals a restricted aggregate growth in aqueous media into spherical nanoparticles and a non-restricted 2D-nanosheet formation in non-polar media. These findings are attributed to a considerably more efficient solvation and, in turn, increased steric demand of the hydrophilic chains in aqueous media than in nonpolar media, which can be explained by the entrapment of water molecules in the hydrophilic aggregate shellviahydrogen bonds. Our findings reveal that the different solvation of peripheral solubilizing groups in solvents of opposed polarity is an efficient method for morphology control in self-assembly

Attogram sensing of trinitrotoluene with a self-assembled molecular gelator

Detection of explosives is of utmost importance due to the threat to human security as a result of illegal transport and terrorist activities. Trinitrotoluene (TNT) is a widely used explosive in landmines and military operations that contaminates the environment and groundwater, posing a threat to human health. Achieving the detection of explosives at a sub-femtogram level using a molecular sensor is a challenge. Herein we demonstrate that a fluorescent organogelator exhibits superior detection capability for TNT in the gel form when compared to that in the solution state. The gel when coated on disposable paper strips detects TNT at a record attogram (ag, 10–18 g) level (∼12 ag/cm2) with a detection limit of 0.23 ppq. This is a simple and low-cost method for the detection of TNT on surfaces or in aqueous solutions in a contact mode, taking advantage of the unique molecular packing of an organogelator and the associated photophysical properties

Solvent-directed self-assembly of π gelators to hierarchical macroporous structures and aligned fiber bundles

Morphology variation: The Boc-alanine linked OPV exhibits an unprecedented formation of periodic macroporous honeycomb structures in chloroform and aligned fiber bundles in toluene (see SEM images). This represents a unique example for a distinct morphology change of an organogelator from macroporous honeycomb to aligned fiber bundles upon changing the solvent

Understanding the role of conjugation length on the self-assembly behaviour of oligophenyleneethynylenes

Oligophenyleneethynylenes (OPEs) are prominent building blocks with exciting optical and supramolecular properties. However, their generally small spectroscopic changes upon aggregation make the analysis of their self-assembly challenging, especially in the absence of additional hydrogen bonds. Herein, by investigating a series of OPEs of increasing size, we have unravelled the role of the conjugation length on the self-assembly properties of OPEs

Kontrolle über Selbstassemblierung durch Ausnutzung von Koordinationsisomerie

Hierin wird die inhärente geometrische Isomerie eines PtII Komplexes als neues Werkzeug zur Kontrolle von supramolekularen Assemblierungsprozessen ausgenutzt. Bestrahlung mit UV‐Licht sowie die sorgfältige Auswahl des verwendeten Lösungsmittels, der Temperatur und Konzentration führen zu einer regelbaren Koordinationsisomerie. Dies ermöglicht ein vollständig reversibles Schalten zwischen zwei definierten aggregierten Spezies (1D Fasern ↔ 2D Lamellen) mit unterschiedlichem photoresponsivem Verhalten. Unsere Erkenntnisse erweitern nicht nur die Reichweite von Koordinationsisomerie, sondern eröffnen auch aufregende Möglichkeiten zur Entwicklung neuartiger stimuliresponsiver Materialien

Exploiting Coordination Isomerism for Controlled Self-Assembly

We exploited the inherent geometrical isomerism of a PtII complex as a new tool to control supramolecular assembly processes. UV irradiation and careful selection of solvent, temperature, and concentration leads to tunable coordination isomerism, which in turn allows fully reversible switching between two distinct aggregate species (1D fibers↔2D lamellae) with different photoresponsive behavior. Our findings not only broaden the scope of coordination isomerism, but also open up exciting possibilities for the development of novel stimuli-responsive nanomaterials

Kontrolle über Selbstassemblierung durch Ausnutzung von Koordinationsisomerie

Hierin wird die inhärente geometrische Isomerie eines PtII Komplexes als neues Werkzeug zur Kontrolle von supramolekularen Assemblierungsprozessen ausgenutzt. Bestrahlung mit UV‐Licht sowie die sorgfältige Auswahl des verwendeten Lösungsmittels, der Temperatur und Konzentration führen zu einer regelbaren Koordinationsisomerie. Dies ermöglicht ein vollständig reversibles Schalten zwischen zwei definierten aggregierten Spezies (1D Fasern ↔ 2D Lamellen) mit unterschiedlichem photoresponsivem Verhalten. Unsere Erkenntnisse erweitern nicht nur die Reichweite von Koordinationsisomerie, sondern eröffnen auch aufregende Möglichkeiten zur Entwicklung neuartiger stimuliresponsiver Materialien

Attogram Sensing of Trinitrotoluene with a Self-Assembled Molecular Gelator

Detection of explosives is of utmost importance due to the threat to human security as a result of illegal transport and terrorist activities. Trinitrotoluene (TNT) is a widely used explosive in landmines and military operations that contaminates the environment and groundwater, posing a threat to human health. Achieving the detection of explosives at a sub-femtogram level using a molecular sensor is a challenge. Herein we demonstrate that a fluorescent organogelator exhibits superior detection capability for TNT in the gel form when compared to that in the solution state. The gel when coated on disposable paper strips detects TNT at a record attogram (ag, 10^–18 g) level (∼12 ag/cm²) with a detection limit of 0.23 ppq. This is a simple and low-cost method for the detection of TNT on surfaces or in aqueous solutions in a contact mode, taking advantage of the unique molecular packing of an organogelator and the associated photophysical properties