Interplay of Interactions Governing the Dynamic Conversions of Acyclic and Macrocyclic Helicates

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TitleInterplay of Interactions Governing the Dynamic Conversions of Acyclic and Macrocyclic Helicates
Publication TypeJournal Article
Year of Publication2009
AuthorsCampbell, VE, de Hatten X, Delsuc N, Kauffmann B, Huc I, Nitschke JR
JournalChemistry-a European Journal
Volume15
Issue25
Pagination6138-6142
ISBN Number0947-6539
Accession NumberISI:000267501400009
Abstract

A rigid, helical macrocycle that contains two copper(I) ions has been synthesized through subcomponent self-assembly. Although it does not obey the "rule of coordinative saturation", this macrocycle could be prepared through subcomponent substitution starting from a tri(copper(I)) helicate, in a reaction in which copper(I) was ejected. The macrocycle was observed to readily participate in a sequence of transformations between helical structures mediated by the electronic effects of substituents, entropic effects, the conformational preferences of organic building blocks, and the coordinative preferences of the metal ion. The thermodynamic parameters governing the interconversion of an "open" helicate and the "closed" macrocycle were determined through van 't Hoff analysis, allowing quantification of the entropic driving force for macrocyclization.

URL<Go to ISI>://000267501400009
DOI10.1002/chem.200900693
Short TitleInterplay of Interactions Governing the Dynamic Conversions of Acyclic and Macrocyclic Helicates
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