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Mutual complexation between π-π stacked molecular tweezers

DOI: 10.1021/acs.cgd.7b01376 DOI Help

Authors: Matthew Parker (University of Reading) , Claire A. Murray (University of Reading) , Lewis R. Hart (University of Reading) , Barnaby W. Greenland (University of Reading) , Wayne Hayes (University of Reading) , Christine J Cardin (University of Reading) , Howard Matthew Colquhoun (University of Reading)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Crystal Growth & Design

State: Published (Approved)
Published: December 2017
Diamond Proposal Number(s): 7786

Abstract: Aromatic and heterocyclic molecules which form electronically-complementary π-π stacked complexes have recently found extensive application in functional materials, molecular machines, and stimuli-responsive supramolecular polymers. Here we describe the design and synthesis of model compounds that self-assemble through complementary stacking motifs, paralleling those postulated to exist in high-molecular weight, healable, supramolecular polymer systems. Complexation studies using 1H NMR and UV-vis spectroscopy indicated formation of a complementary complex between a π-electron rich di-pyrenyl tweezer-motif and a tweezer-like, π electron deficient bis-diimide. The binding stoichiometry in solution between the chain folding diimide and the pyrenyl derivative was equimolar with respect to the two binding motifs and the resulting association constant was measured at Ka = 1200 ± 90 M-1. Single crystal X-ray analysis of this "tweezer-tweezer" complex showed a low-energy conformation of the triethylenedioxy linker within the bis-diimide chain-fold. Interplanar separations of 3.4 – 3.5 Å were found within the pi-stacks, and supporting hydrogen bonds between pyrenyl amide NH groups and diimide carbonyl oxygens were identified.

Subject Areas: Chemistry


Instruments: I19-Small Molecule Single Crystal Diffraction