Counteranion‐ and Solvent‐Mediated Chirality Transfer in the Supramolecular Polymerization of Luminescent Platinum(II) Complexes

Abstract

The chirality of supramolecular polymeric materials is subtly affected by a delicate balance among various non‐covalent interactions, the details of which are inadequately understood. Now, a fine balance of intermolecular interactions, including closed‐shell metal–metal, dispersive and electrostatic interactions, is used to direct the delicate orientation of monomeric building blocks, thereby achieving the successful preparation of different nanostructures with distinct supramolecular chirality. Moreover, kinetically trapped and thermodynamically stable aggregates were monitored over time in the supramolecular polymerization of cationic PtII complexes. The dynamic self‐assembly process can be successfully controlled by modifying the counteranion and solvent composition. A chiral doping approach can also be used to induce the chirality of an achiral PtII complex at the supramolecular level.

Controlled Supramolecular Polymerization of d8 Metal Complexes through Pathway Complexity and Seeded Growth

“…Thus, this elegant example highlights the strong influence exerted by counterions on the kinetic vs. thermodynamic pathways of metal-containing self-assembled systems. In another work, [37] the same group has shown a related phenomenon for the chiral Pt(II) complexes 11 a, 11 b and 11 c (Figure 7a) using the same counteranions as the previous report. Among them, 11 a and 11 b with counteranions PF 6 À and OTf À respectively, can form stable aggregates.…”

Solute–Solvent Interactions in Modern Physical Organic Chemistry: Supramolecular Polymers as a Muse

“…A similar effect was also found for platinum metallosupramolecular polymers, although the structural transitions between 10 and 25 vol % acetonitrile were attributed to different stabilization of the dipoles in the various polymer morphologies. 201 As such, these examples strongly indicate that the formation of microscopically phase-separated domains in aqueous mixtures may be an important aspect of stabilizing or destabilizing interactions in supramolecular polymerizations in water.…”

Multinuclear PtII Complexes: Why Three is Better Than Two to Enhance Photophysical Properties

“…[6,11,[29][30][31] Thus, the shorter the distance is, the stronger the electronic Pt•••Pt electronic interaction is, and the more bathochromically shiftedt he MMLCT band is. [32][33] However,t he formation of assembled speciesn ot only changes the absorption and emission energy, but also leads often to an enhancement of the emission quantum yields (PLQY) and to an elongationo ft he excited state lifetime, due to ac hange of the nature of the lowest transitiona nd the increasing rigidity of the packed units. [20] Ourg roup has recently reported ap hosphorescent mononuclear amphiphilic Pt II -complex [20] (PLQY of 1% in aerated dioxane) capable of producing strong orange phosphorescence with aP LQY up to 84 %i nw ater/dioxane (95:5) solution.…”