Exploiting Coordination Isomerism for Controlled Self‐Assembly

Abstract

Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.

Tuning Aqueous Supramolecular Polymerization by an Acid‐Responsive Conformational Switch

“…Given that the trans ‐form of 1 is the major species formed in solution, we can assume that only this more stable and preorganized conformation is able to engage in supramolecular polymerization, whereas the less stable, distorted cis ‐form is present, if at all, only in trace amounts. A similar behavior has been recently observed for self‐aggregating Pt II complexes undergoing cis‐trans coordination isomerism, where the dormant cis ‐isomer is completely removed from the equilibrium due to the stabilization of the aggregation‐active trans ‐form by aggregation and solvation effects. A similar stabilization of the trans ‐state is expected here.…”

Morphology control in metallosupramolecular assemblies through solvent-induced steric demand

“…As previously shown by our group, [16][17][18] the combination of an amide group with a central M(Pd,Pt)Cl 2 moiety is a highly self-recognizing intermolecular hydrogen-bonding pattern to drive supramolecular polymerisation. In addition, our molecular design features peripheral triethylene glycol (TEG) chains, leading to a bolaamphiphilic structure.…”

“…Based on our experience with an analogous hydrophobic Pt(II) complex bearing an azobenzene moiety, 18 we initially probed the coordination isomerism of C1. To this end, we prepared five separate solutions of C1 in solvents of different polarity ( Fig.…”

“…This observation suggests the dormant nature of the assemblies to light irradiation, similar to a previously reported structurally related compound. 18 Unravelling the supramolecular packing of C1 in non-polar media…”

Consequences of hidden kinetic pathways on supramolecular polymerization

“…4a), suggesting the formation of hydrogen bonds. 19,[42][43][44] Most strikingly, the resonance corresponding to the gallic protons is deshielded in contrast to all other aromatic signals. This is suggestive of the gallic proton interacting with an electron withdrawing moiety, most likely via an unconventional hydrogen bonding interaction (C arom -H/X).…”