Chiral Truxene-Based Self-Assembled Cages: Triple Interlocking and Supramolecular Chirogenesis.

Incorporating chiral elements in host-guest systems currently attracts much attention because of the major impact such structures may have in a wide range of applications, from pharmaceuticals to materials science and beyond. Moreover, the development of multi-responsive and -functional systems is highly desirable since they offer numerous benefits. In this context, we describe herein the construction of a metal-driven self-assembled cage that associates a chiral truxene-based ligand and a bis-ruthenium complex. The maximum separation between both facing chiral units in the assembly is fixed by the intermetallic distance within the lateral bis-ruthenium complex (8.4 Å). The resulting chiral cavity was shown to encapsulate polyaromatic guest molecules, but also to afford a chiral triply interlocked [2]catenane structure. The formation of the latter occurs at high concentration, while its disassembly could be achieved by the addition of a planar achiral molecule. Interestingly the planar achiral molecule exhibits induced circular dichroism signature when trapped within the chiral cavity, thus demonstrating the ability of the cage to induce supramolecular chirogenesis.

Investigations of the Photothermal Properties of a Series of Molecular Gold-bis(dithiolene) Complexes Absorbing in the NIR-III Region.

The photothermal properties of a series of neutral radical gold-bis(dithiolene) complexes absorbing in the near-infrared-III window (1550-1870 nm) have been investigated. This class of complexes was found to be good photothermal agents (PTAs) in toluene under 1600 nm laser irradiation with photothermal efficiencies around 40 and 60 % depending on the nature of the dithiolene ligand. To the best of our knowledge, these complexes are the first small molecular photothermal agents to absorb so far into the near infrared. To test their applicability in water, these hydrophobic complexes have been encapsulated into nanoparticles constituted by amphiphilic block-copolymers. Stable suspensions of polymeric nanoparticles (NPs) encapsulating the gold-bis(dithiolene) complexes have been prepared which show a diameter around 100 nm. The encapsulation rate was found to be strongly dependent on the nature of the dithiolene ligands. The photothermal properties of the aqueous suspensions containing gold-bis(dithiolene) complexes were then studied under 1600 nm laser irradiation. These studies demonstrate that water has strong photothermal activity in the NIR-III region that, cannot be overcome even with the addition of gold complexes displaying good photothermal properties.