Circularly-Polarized Luminescence (CPL) from Chiral AIE Molecules and Macrostructures.

Circularly-polarized luminescence (CPL) has received new attention on the rise of applications to generate devices and biologically active probes. These applications require fluorophores that are not only chiral but also provide strong fluorescence intensity in aggregated state. Thus, a new research branch has opened up a few years ago, which allows CPL-active fluorophores to be emissive in aggregated-state. As a result, reports on the combination of the CPL property with the aggregation-induced emission (AIE) phenomenon have emerged. Herein the early design principles that have been reported until now to generate CPL-active AIE-active fluorophores (AIEgens) are summarized. In this regard the alignment of monomeric emitters in a chiral fashion, either in supramolecules, polymers or liquid crystals has been proven to be a successful approach. Additionally, first reports have appeared that demonstrate how to tackle the daunting task to furnish individual CPL-active AIEgens.

Aggregation-induced emissive nanoparticles for fluorescence signaling in a low cost paper-based immunoassay.

Low cost paper based immunoassays are receiving interest due to their fast performance and small amounts of biomolecules needed for developing an immunoassay complex. In this work aggregation-induced emissive (AIE) nanoparticles, obtained from a diastereoisomeric mixture of 1,2-di-(4-hydroxyphenyl)-1,2-diphenylethene (TPEDH) in a one-step top-down method, are characterized through Dynamic Light Scattering (DLS), Scanning Electron Microscopy (SEM), and Zeta potential. By measuring the Zeta potential before and after labeling the nanoparticles with antibodies we demonstrate that the colloidal system is stable in a wide pH-range. The AIE-active nanoparticles are deposited on chitosan and glutaraldehyde modified paper pads overcoming the common aggregation-caused quenching (ACQ) effect. Analyte concentrations from 1000ng and below are applied in a model immunocomplex using Goat anti-Rabbit IgG and Rabbit IgG. In the range of 7.81ng-250ng, linear trends with a high R(2) are observed, which leads to a strong increase of the blue fluorescence from the TPEDH nanoparticles.

A colour-tunable chiral AIEgen: reversible coordination, enantiomer discrimination and morphology visualization.

We present a conceptually new approach to synthesise a boron-containing Aggregation-Induced Emissive Luminogen (AIEgen) with a chiral chromophore. An intramolecular N-B coordinating bond results in a low-energy transition that renders the material red-emissive in a solid state. By competitive binding of nucleophiles to the boron atom, this bond is replaced in favour of an intermolecular coordinating bond, which results in a tremendous blue-shift in both the absorption and emission. A supportive DFT computation elucidates that a breakage of the intramolecular N-B coordinating bond causes a tremendous loss of conjugation in the LUMO, resulting in a larger energy gap. Owing to the fact that our scaffold is intrinsically chiral and Lewis-acidic, we demonstrate how our AIEgen discriminates between two pairs of enantiomers in a simple UV-vis measurement. Furthermore, the binding capabilities are exploited to stain polymer blends that comprised a non-coordinating and a Lewis-basic polymer. The red fluorescence that originates only from domains of the non-coordinating polymer is conveniently detected by a fluorescence microscope. Thus, compared to current analytical methods, we present a cheaper and faster methodology to study the micro-morphologies of certain polymer blends.

A Luminescent Nitrogen-Containing Polycyclic Aromatic Hydrocarbon Synthesized by Photocyclodehydrogenation with Unprecedented Regioselectivity.

We present a nitrogen-containing polycyclic aromatic hydrocarbon (N-PAH), namely 12-methoxy-9-(4-methoxyphenyl)-5,8-diphenyl-4-(pyridin-4-yl)pyreno[1,10,9-h,i,j]isoquinoline (c-TPE-ON), which exhibits high quantum-yield emission both in solution (blue) and in the solid state (yellow). This molecule was unexpectedly obtained by a three-fold, highly regioselective photocyclodehydrogenation of a tetraphenylethylene-derived AIEgen. Based on manifold approaches involving UV/Vis, photoluminescence, and NMR spectroscopy as well as HRMS, we propose a reasonable mechanism for the formation of the disk-like N-PAH that is supported by density functional theory calculations. In contrast to most PAHs that are commonly used, our system does not suffer from entire fluorescence quenching in the solid state due to the peripheral aromatic rings preventing π-π stacking interactions, as evidenced by single-crystal X-ray analysis. Moreover, its rod-like microcrystals exhibit excellent optical waveguide properties. Hence, c-TPE-ON comprises a N-PAH with unprecedented luminescent properties and as such is a promising candidate for fabricating organic optoelectronic devices. Our design and synthetic strategy might lead to a more general approach to the preparation of solution- and solid-state luminescent PAHs.

Chirality transfer in 1D self-assemblies: influence of H-bonding vs metal coordination between dicyano[7]helicene enantiomers.

Chiral recognition as well as chirality transfer in supramolecular self-assembly and on-surface coordination is studied for the enantiopure 6,13-dicyano[7]helicene building block. It is remarkable that, with this helical molecule, both H-bonded chains and metal-coordinated chains can be formed on the same substrate, thereby allowing for a direct comparison of the chain bonding motifs and their effects on the self-assembly in experiment and theory. Conformational flexure and both adsorbate/adsorbent and intermolecular interactions can be identified as factors influencing the chiral recognition at the binding site. The observed H-bonded chains are chiral, however, the overall appearance of Cu-coordinated chains is no longer chiral. The study was performed via scanning tunneling microscopy, X-ray-photoelectron spectroscopy and density functional theory calculations. We show a significant influence of the molecular flexibility and the type of bonding motif on the chirality transfer in the 1D self-assembly.

Structural manipulation of colloidal silica.

Structural properties of the nanosized silica Ludox TMA with novel functionalizations have been investigated. Silica is stabilized in aqueous solution at a pH value higher than the pK(a) of silicic acid. A surface modification consisting of poly(p-benzamide)s functionalized with derivatized nucleobases on the C-terminus and cationic pyridinium functions on the N-terminus of the polymer chain was carried out. Due to the negatively charged surface, strong physisorption of the cationic pyridinium functions occurs. It is possible to stabilize diluted solutions of silica without agglomeration in solvents with various polarities by using pyridinium cations. Defined structures could be created according to the hydrogen donor/acceptor potential of the introduced nucleobase. Surprisingly the interactions between the same nucleobases are already sufficient for strong particle-particle interactions. Dramatic effects on the structural behavior are characterized by PCS, (S)TEM and EFTEM.