Molecular meccano, 57: Template-directed syntheses, spectroscopic properties, and electrochemical behavior of [n]catenanes

Abstract

Catenanes composed of two, three, five, or seven interlocked macrocycles have been synthesized in yields ranging from 1 to 30%. Their template- directed syntheses rely on a series of cooperative noncovalent bonding interactions between π-electron rich 1,5-dioxynaphthalene ring systems and π-electron deficient bipyridinium units which are incorporated within the macrocyclic components. The interlocked structure associated with one of the [3]catenanes was demonstrated unequivocally by single crystal X-ray analysis which also revealed the formation of polar stacks stabilized by intermolecular [π···π] interactions. The number of interlocked components of each catenane was determined by liquid secondary ion, matrix- assisted laser desorption ionization/time-of-flight, and/or electrospray mass spectrometries. The absorption spectra, emission spectra, and electrochemical properties of the macrocyclic components and of the catenanes have been investigated. Two kinds of charge-transfer absorption bands (intramolecular in the cyclophanes containing electron-donor and electron-acceptor units, intercomponent in the catenanes) have been found. Such charge-transfer excited states are responsible for the quenching of the potentially fluorescence units of the cyclophanes, and of the crown ethers in the catenanes. Charge-transfer electronic interactions are also evidenced by the electrochemical behavior. Correlations among the redox potentials of the various compounds are reported and discussed.