ABSTRACT
A strategy is presented to improve the excited state reactivity of homoleptic copper-bis(diimine) complexes CuL2 + by increasing the steric bulk around CuI whereas preserving their stability. Substituting the phenanthroline at the 2-position by a phenyl group allows the implementation of stabilizing intramolecular π stacking within the copper complex, whereas tethering a branched alkyl chain at the 9-position provides enough steric bulk to rise the excited state energy E00 . Two novel complexes are studied and compared to symmetrical models. The impact of breaking the symmetry of phenanthroline ligands on the photophysical properties of the complexes is analyzed and rationalized thanks to a combined theoretical and experimental study. The importance of fine-tuning the steric bulk of the N-N chelate in order to stabilize the coordination sphere is demonstrated. Importantly, the excited state reactivity of the newly developed complexes is improved as demonstrated in the frame of a reductive quenching step, evidencing the relevance of our strategy.
ABSTRACT
Nanoassemblies encompass a large variety of systems (organic, crystalline, amorphous and porous). The nanometric size enables these systems to interact with biological entities and cellular organelles of similar dimensions (proteins, cells, ). Over the past 20 years, the exploitation of their singular properties as contrast agents has led to the improvement of medical imaging. The use of nanoprobes also allows the combination of several active units within the same nanostructure, paving the way to multi-imaging. Thus, the nano-object provides various additional information which helps simplify the number of clinical procedures required. In this review, we are interested in the combination between fluorescent units and magnetic nanoparticles to perform dual-mode magnetic resonance imaging (MRI) and fluorescent imaging. The effect of magnetic interaction in multicore iron oxide nanoparticles on the MRI contrast agent properties is highlighted.
