Miguel Petrielli

TUTORIAL REVIEW

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Anion templated assembly of mechanically interlocked structures
Matthew S. Vickers and Paul D. Beer*
Received 7th July 2006 First published as an Advance Article on the web 5th December 2006 DOI: 10.1039/b518077p This tutorial review describes the evolution of the field of chemical templation, in particular, emphasising the impactits application has made to the synthesis of mechanically interlocked structures. Recent advances in the use of negatively charged template species for the synthesis of interlocked structures are detailed, with the main focus of this review describing the development of a general anion templation strategy that combines anion recognition with ion-pairing. The versatility of this methodology isdemonstrated by the chloride anion templated synthesis of a series of interpenetrated pseudorotaxane, rotaxane and catenane structures. Upon template removal, the mechanically interlocked rotaxanes and catenanes are shown to bind anions within their topologically unique anion binding clefts by virtue of electrostatic and hydrogen bonding interactions, exhibiting a strong selectivity for the chloridehalide anion template. The incorporation of the photo-active rhenium(I) bipyridyl signalling group into the rotaxane structural framework highlights the potential of these interlocked systems in future chemical sensor design.

1. Introduction
We are all familiar with everyday examples of templates as models for making a variety of diverse objects. Indeed, the Oxford English Dictionarydefinition of a template is ‘‘a
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shaped piece of rigid material used as a pattern for processes such as cutting out, shaping, or drilling’’. The concept of templation is equally applicable to the molecular scale and the formative example of the concept came from Busch’s metal ion templated macrocycle syntheses during the 1960’s. In recentyears, the increasingly detailed study of biological systems has provided the inspiration for the synthesis of a huge variety of

Matthew Vickers was born in Plymouth, Devon, and graduated from Oxford University in 2003 with a 1st class honours degree in Chemistry. Following a successful final year undergraduate research project, he remained in Oxford to study towards a DPhil under thesupervision of Professor Paul Beer and is currently in the final year of his studies. During his time in Oxford, Matthew has been a member of Keble College and received an underMatthew S. Vickers graduate scholarship in 2000 as well as a graduate scholarship in 2003. His research interests are in the area of supramolecular chemistry and include the topics of molecular recognition and anion templation.Paul Beer was born in Totnes, Devon, and gained a first class honours degree in chemistry from King’s College, London, in 1979. He remained there to receive a PhD (1979–1982) in the area of organophosphorus chemistry, under the supervision of Dr C. Dennis Hall. A Royal Society European postdoctoral fellowship (1982–1983) enabled him to conduct research in supramolecular chemistry with ProfessorJean-Marie Lehn at the Universite Louis Pasteur, Strasbourg, France. After a demon´ stratorship at the University of Exeter (1983–1984) he took up a
This journal is ß The Royal Society of Chemistry 2007

New Blood Lectureship at the University of Birmingham in 1984. In 1990 he moved to th e Ino rgan ic Che mistry Laboratory, University of Oxford, where he is also a tutorial fellow at Wadham College.He became a Professor of Chemistry in 1998. He was awarded the Royal Society of Chemistry Meldola Medal in 1987, the UNESCO Javed Husain prize in 1993, the Royal Society of Chemistry CordayPaul D. Beer Morgan Medal in 1994 and the Royal Society of Chemistry Tilden Lectureship and Medal in 2004. Professor Beer is author of over 280 research papers including a book, co-authored with previous...