Despite established clinical utilisation, there is an increasing need for safer, more inert gadolinium-based contrast agents, and for chelators that react rapidly with radiometals. Here we report the syntheses of a series of chiral DOTA chelators and their corresponding metal complexes and reveal properties that transcend the parent DOTA compound. We incorporated symmetrical chiral substituents around the tetraaza ring, imparting enhanced rigidity to the DOTA cavity, enabling control over the range of stereoisomers of the lanthanide complexes. The Gd chiral DOTA complexes are shown to be orders of magnitude more inert to Gd release than [GdDOTA]−. These compounds also exhibit very-fast water exchange rates in an optimal range for high field imaging. Radiolabeling studies with (Cu-64/Lu-177) also demonstrate faster labelling properties. These chiral DOTA chelators are alternative general platforms for the development of stable, high relaxivity contrast agents, and for radiometal complexes used for imaging and/or therapy.

A versatile π-extension reaction was developed based on the three-component cross-coupling of aryl halides, 2-haloarylcarboxylic acids, and norbornadiene. The transformation is driven by the direction and subsequent decarboxylation of the carboxyl group, while norbornadiene serves as an ortho-C-H activator and ethylene synthon via a retro-Diels-Alder reaction. Comprehensive DFT calculations were performed to account for the catalytic intermediates.

The self-assembly of lanthanide (europium or lanthanium) bimetallic triple helicates from two closely related chiral ligands resulted in a very different supramolecular phenomenon. One gave rise to significantly diastereoselective formation of a triple helicate, whereas the other led to diastereoselective breaking to generate a mixture of P and M diastereomers in ∼1 : 1.1 ratio. The first X-ray crystal structure of a chiral ligand based lanthanide triple-helicate indicates that successive CH-π interactions were found to maintain the supramolecular helical structure.

The coordination of AlCl(3) by the complex [{MeAl(2-py)(3)}Li.thf] () gives the unusual product [{MeAl(2-py)(3)}(2)Al](+)[{MeAl(2-py)(3)}Li](2)(mu-Cl)(-) (), in which the [MeAl(2-py)(3)](-) aluminate anion of acts cooperatively in the coordination of an Al(3+) cation and Cl(-) anion.

Chirality is ubiquitous within biological systems where many of the roles and functions are still undetermined. Given this,there is aclear need to design and develop sensitive chiral optical probes that can function within ab iological setting.Here we report the design and synthesis of magnetically responsive Circularly Polarized Luminescence (CPL) complexes displaying exceptional photophysical properties (quantum yield up to 31 %a nd j g lum j up to 0.240) by introducing chiral substituents onto the macrocyclic scaffolds.M agnetic CPL responses are observed in these chiral Eu III complexes, promoting an exciting development to the field of magnetooptics.The j g lum j of the 5 D 0 ! 7 F 1 transition increases by 20 % from 0.222 (0 T) to 0.266 (1.4 T) displaying al inear relationship between the Dg lum and the magnetic field strength. These Eu III complexes with magnetic CPL responses,p rovides potential development to be used in CPL imaging applications due to improved sensitivity and resolution.