Steve Comby

The synthesis of a family of chiral and enantiomerically pure pyridyl‐diamide (pda) ligands that upon complexation with europium [Eu(CF₃SO₃)₃] result in chiral complexes with metal centered luminescence is reported; the sets of enantiomers giving rise to both circular dichroism (CD) and circularly polarized luminescence (CPL) signatures. The solid‐state structures of these chiral metallosupramolecular systems are determined using X‐ray diffraction showing that the ligand chirality is transferred from solution to the solid state. This optically favorable helical packing arrangement is confirmed by recording the CPL spectra from the crystalline assembly by using steady state and enantioselective differential chiral contrast (EDCC) CPL Laser Scanning Confocal Microscopy (CPL‐LSCM) where the two enantiomers can be clearly distinguished.

Organic–inorganic core–shell nanocomposites have attracted increasing attention for applications in imaging, controlled release, biomedical scaffolds and self-healing materials. While tunable properties can readily be achieved through the selection of complementary building blocks, synergistic enhancement requires management of the core–shell interface. In this work, we report a one-pot method to fabricate hybrid core–shell nanocomposite particles (CSNPs) based on ureasils. The native structure of ureasils, which are poly(oxyalkylene)/siloxane hybrids, affords formation of an organic polymer core via nanoprecipitation, while the terminal siloxane groups act as a template for nucleation and growth of the silica shell via the Stöber process. Through optimisation of the reaction conditions, we demonstrate the reproducible synthesis of ureasil CSNPs, with a hydrodynamic diameter of ∼150 nm and polydispersity 50 days. Selective functionalisation, either through the physical entrapment of polarity-sensitive fluorescent probes (coumarin 153, pyrene) or covalent-grafting to the silica shell (fluorescein isothiocyanate) is also demonstrated and provides insight into the internal environment of the particles. Moreover, preliminary studies using a live/dead cell assay indicate that ureasil CSNPs do not display cytotoxicity. Given the simple fabrication method and the structural tunability and biocompatability of the ureasils, this approach presents an efficient route to multifunctional core–shell nanocomposite particles whose properties may be tailored for a targeted application.

The formation, stability constants and luminescence of chiral Eu(iii) supramolecular assemblies were studied in CH₃CN.

The development of material‐supported molecular logic gate mimics (MGLMs) for contained application and device fabrication has become of increasing interest. Herein, we present the formation of ≈5 nm gold nanoparticles (AuNPs) that have been surface‐modified (via a thiol linkage) with heptadentate cyclen‐based complexes of europium and terbium for sensing applications using delayed lanthanide luminescence and as integrated logic gate mimics within competitive media.

Herein, we have developed a white-light-emitting system based on the formation of discrete lanthanide-based self-assembled complexes using a newly-designed ligand. We demonstrate that fine tuning of the lanthanide ions molar ratio in the self-assemblies combined with the intrinsic blue fluorescence of the ligand allows for the successful emission of pure white light with CIE coordinates of (0.33, 0.34).

The synthesis of coordinatively unsaturated tetra-substituted 1,4,7,10-tetraazacyclododecane (cyclen) lanthanide complexes is described; these structures, possessing hydrophobic (C₁₂-alkyl) tails and hydrophilic head groups, self-assemble into supramolecular micellar structures in aqueous solution, and hence can be utilised as novel contrast agents for MRI.

Luminescent solar concentrators (LSCs) offer significant potential for solar energy capture in the urban environment. Here, the first example of a planar, doped LSC using Lumogen Red (LR305) as the luminophore and a di‐ureasil organic–inorganic hybrid as the waveguide is reported. The di‐ureasil waveguide offers several advantages over organic polymer waveguides including facile solution‐processing from benign solvents and extension of the absorption window through energy transfer. Spectral evaluation using absorption and photoluminescence spectroscopies is used to optimize the LSC composition, yielding optical efficiencies as high as 14.5% (300–800 nm). A power conversion efficiency (PCE) of 0.54% is obtained for the champion LSC coupled to a c‐Si PV cell using the di‐ureasil precursor as an optical glue to minimize interfacial losses. Finally, a simple figure of merit to evaluate the performance of LSC‐solar cell composite systems is proposed that enables comparison of the actual improvement in the efficiency of solar cells due to the attachment of the LSC, irrespective of the LSC design, architecture or materials. A PCE of 17.4% for the solar cell in the emission region of the LSC is obtained, which is a remarkable improvement of ≈40% over its AM 1.5G value.

The structure-type of a Ho(iii)-based MOF can be varied using a range of different lanthanide ions to tune the photophysical properties and produce ligand-sensitised near-infrared and visible light emitters.