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Template‐Directed Syntheses, Spectroscopic Properties, and Electrochemical Behavior of [ n ]Catenanes
Author(s) -
Ashton Peter R.,
Baldoni Virna,
Balzani Vincenzo,
Claessens Christian G.,
Credi Alberto,
Hoffmann H. D. Andreas,
Raymo Françisco M.,
Stoddart J. Fraser,
Venturi Margherita,
White Andrew J. P.,
Williams David J.
Publication year - 2000
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200004)2000:7<1121::aid-ejoc1121>3.0.co;2-3
Subject(s) - catenane , chemistry , intramolecular force , electron transfer , intermolecular force , electrochemistry , cyclophane , crystallography , photochemistry , electrospray ionization , stereochemistry , molecule , crystal structure , ion , electrode , organic chemistry
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.