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Thermo-/Mechano-Chromic Chiral Coordination Dimer: Formation of Switchable and Metastable Discrete Structure through Chiral Self-Sorting.

Kazuyoshi TakimotoTakumi ShimadaKazuhiko NaguraJonathan P HillTakashi NakanishiHidetaka YugeShinsuke IshiharaJan LabutaHisako Sato
Published in: Journal of the American Chemical Society (2023)
Although strong chiral self-sorting often emerges in extended covalent or supramolecular polymers, the phenomenon is generally weak in discrete assemblies (e.g., dimers and oligomers) of small molecules due to the lack of a cooperative growth mechanism. Consequently, chiral self-sorting has been overlooked in the design of switchable and metastable discrete supramolecular structures. Here, we report a butyl-benzo[ h ]quinoline-based iridium(III) complex (Bu- Ir ) with helical chirality at its metal center, which forms preferentially a homochiral dimer and exhibits thermo-/mechano-chromism based on a monomer-dimer transformation. While a five-coordinate monomer is formed in a racemic or an enantiopure Bu- Ir solution at 25 °C, a six-coordinate homochiral dimer complex is formed almost exclusively at low temperatures, with a higher degree of dimerization in enantiopure Bu- Ir solution. Estimation of apparent dimerization binding constants ( K ) and thermodynamic parameters (Δ H and Δ S ) based on variable temperature ultraviolet-visible (UV-vis) and 1 H NMR spectra reveals a strong preference for homochiral dimerization (largest known value for the coordination complex, K homo / K hetero > 50). Notably, crystals of the homochiral dimer are metastable, undergoing a distinct color change upon grinding (from yellow to red) due to mechanical cleavage of coordination bonds (i.e., a dimer to monomer transformation). A comparison with control compounds having different substituents (proton, methyl, isopropyl, and phenyl groups) reveals that Bu- Ir dimerization involves both strong homochiral self-sorting preference and connected thermo-/mechano-chromic behavior, which is based on matched propeller-shaped chirality and subtle steric repulsion between alkyl substituents that render the homochiral dimer switchable and metastable. These findings provide substantial insights into the emergence of dynamic functionality based on the rational design of discrete chiral assemblies.
Keyphrases
  • ionic liquid
  • capillary electrophoresis
  • magnetic resonance
  • high resolution
  • magnetic resonance imaging
  • dna binding
  • mass spectrometry
  • molecular dynamics
  • aqueous solution