Chirality induction to achiral molecules by silica-coated chiral molecular assemblies.

Hybrid silica-organic nanohelices are used to organize a large variety of nonchiral small organic molecules or inorganic anions to nanometer-sized assemblies. Such chiral organization of achiral molecules induces chiroptical properties as detected by vibrational or electronic circular dichroism (CD), as well as from circularly polarized luminescence (CPL).

Porphyrin-Based Hybrid Nanohelices: Cooperative Effect between Molecular and Supramolecular Chirality on Amplified Optical Activity.

The development of chiral receptors for discriminating the configuration of the analyte of interest is increasingly urgent in view of monitoring pollution in water and waste liquids. Here, we investigate an easy protocol to immobilize the desired non-water-soluble receptors inside a water-dispersible chiral nanoplatform made of silica. This approach induces chirality in the receptors and Here, we investigate an easy protocol to immobilize the desired non-water-soluble receptors inside a water-dispersible chiral nanoplatform made of silica. This approach induces chirality in the receptors and makes the dye@nanohelix system disperse in a suspension of water without aggregation. We noted strong induction and amplification of chiroptical activity in both achiral and chiral (proline-based or hemicucurbituril-based) porphyrin derivatives with and without zinc ions once confined and organized in nanometer silica helices. The results clearly demonstrated that the organization-induced chirality amplification of porphyrins dominates the molecular chirality, and the amplification is more efficient for more flexible porphyrins (especially free-base and achiral).

Luminescence polarization of gold nanoclusters reveals directional self-assembly.

Study of luminescence polarization of spherical nanoclusters arising purely through a self-assembly route has not been explored to date. Here we introduce a gold nanocluster system that explicitly shows luminescence polarization solely through a self-assembly pathway. The directionality involved in the self-assembly governs the luminescence polarization of the nanoclusters. The steady-state and time-resolved emission anisotropy measurements revealed the anisotropically ordered behavior of one-dimensionally self-assembled green emitting nanoclusters. On the contrary, the randomly self-assembled yellow emitting nanoclusters exhibited insignificant luminescence anisotropy.

A self-assembled CdSe QD-organogel hybrid: photophysical and thermoresponsive properties.

A luminescent hybrid gel was prepared by incorporating organic ligand capped CdSe quantum dots (QDs) into a steroid-dimer derived organogel. Photophysical measurements and electron microscopy studies allowed us to understand the nature of the hybrid. Detailed analysis of the excited state dynamics of the hybrid was carried out using a kinetic decay model. The luminescence of the QDs in the hybrid was unaltered by taking it through a gel-sol-gel cycle induced by thermal stimuli. We believe that the results obtained herein provide a route to develop a thermoresponsive device for practical applications, because of the spatial assembly between soft organic scaffolds and colloidal QDs.

Instant room temperature synthesis of self-assembled emission-tunable gold nanoclusters: million-fold emission enhancement and fluorimetric detection of Zn2+ .

Facile synthesis of luminescent metal nanoclusters (NCs) accompanied by emission color tuning is currently an active area of research. In this work we describe a rapid (1 s) room temperature synthesis of luminescent Au NCs from completely nonluminescent NCs through the incorporation of Zn2+. The nanoclusters are initially stabilized by mercaptopropionate, and the coordination of Zn2+ with the carboxylate groups of the ligands rigidifies the Au(i) thiolates restricting the intramolecular rotation-vibrational motion. This significantly reduces the nonradiative relaxation of the excited state to produce yellow luminescent NCs (λem = 580 nm, QY: 6%, τ = 0.2 ms) with almost a million-fold emission enhancement. The enhanced luminescence is due to the self-assembly mediated aggregation induced emission (AIE) of NCs. These NCs on aging for 24 hours transform to highly ordered green emitting NCs (λem = 500 nm, QY: 20%, τ = 20 ns). The blue shift in emission is due to the dominance of inter Au(i)-Au(i) interaction and inter-NC Zn2+ interaction over the intra modes. TEM images show this distinct transition, a decrease in inter NC distance with increased self-assembly. Excited state relaxation dynamics associated with Au(i) thiolate shell dynamics in yellow and green emitting NCs is explained based on the time resolved fluorescence study. The rapid formation of luminescent NCs from nl-NCs has been used for efficient visual and fluorimetric detection of Zn2+.