Mutual complexation between π−π stacked molecular tweezers

Parker, Matthew P, Murray, Claire A, Hart, Lewis R, Greenland, Barnaby W, Hayes, Wayne, Cardin, Christine J and Colquhoun, Howard M (2018) Mutual complexation between π−π stacked molecular tweezers. Crystal Growth & Design, 18 (1). pp. 386-392. ISSN 1528-7483

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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 supra- molecular polymers. Here we describe the design and synthesis of model compounds that self-assemble through complemen- tary 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 dipyrenyl 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 π-stacks, and supporting hydrogen bonds between pyrenyl amide NH groups and diimide carbonyl oxygens were identified.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry > QD0241 Organic chemistry
Q Science > QD Chemistry > QD0901 Crystallography
Depositing User: Barnaby Greenland
Date Deposited: 07 Feb 2018 16:12
Last Modified: 08 Feb 2018 13:43
URI: http://sro.sussex.ac.uk/id/eprint/73406

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