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RISS 인기검색어
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- 저자 : Avestro, Alyssa-Jennifer (검색결과 2 건)
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Cooperative self-assembly: producing synthetic polymers with precise and concise primary structures
Avestro, Alyssa-Jennifer,Belowich, Matthew E.,Stoddart, J. Fraser The Royal Society of Chemistry 2012 Chemical Society reviews Vol.41 No.18
<P>The quest to construct mechanically interlocked polymers, which present precise monodisperse primary structures that are produced both consistently and with high efficiencies, has been a daunting goal for synthetic chemists for many years. Our ability to realise this goal has been limited, until recently, by the need to develop synthetic strategies that can direct the formation of the desired covalent bonds in a precise and concise fashion while avoiding the formation of unwanted kinetic by-products. The challenge, however, is a timely and welcome one, as a consequence of, primarily, the potential for mechanically interlocked polymers to act as dynamic (noncovalent) yet robust (covalent) new materials for a wide array of applications. One such strategy which has been employed widely in recent years to address this issue, known as Dynamic Covalent Chemistry (DCC), is a strategy in which reactions operate under equilibrium and so offer elements of “proof-reading” and “error-checking” to the bond forming and breaking processes such that the final product distribution always reflects the thermodynamically most favourable compound. By coupling DCC with template-directed protocols, which utilise multiple weak noncovalent interactions to pre-organise and self-assemble simpler small molecular precursors into their desired geometries prior to covalent bond formation, we are able to produce compounds with highly symmetric, robust and complex topologies that are otherwise simply unobtainable by more traditional methods. Harnessing these strategies in an iterative, step-wise fashion brings us ever so much closer towards perfecting the controlled synthesis of high order main-chain mechanically interlocked polymers. This <I>tutorial review</I> focuses (i) on the development of DCC—namely, the formation of dynamic imine bonds—used in conjunction with template-directed protocols to afford a variety of mechanically interlocked molecules (MIMs) and ultimately (ii) on the synthesis of highly ordered poly[<I>n</I>]rotaxanes with high conversion efficiencies.</P> <P>Graphic Abstract</P><P>Emergent positive cooperativity accelerates the efficient template-directed assembly of mechanically interlocked molecules with contiguous [π···π] stacks in high yields. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c2cs35167f'> </P>
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The Chameleonic Nature of Diazaperopyrenium Recognition Processes
Basuray, Ashish N.,Jacquot ,de ,Rouville, Henri‐,Pierre,Hartlieb, Karel J.,Kikuchi, Takashi,Strutt, Nathan L.,Bruns, Carson J.,Ambrogio, Michael W.,Avestro, Alyssa‐,Jennifer,Sc WILEY‐VCH Verlag 2012 Angewandte Chemie Vol.124 No.47
<P><B>Zwei zum Preis von einem</B>: Das Diazaperopyrenium‐Dikation verhält sich sowohl homo‐ als auch heterophil, indem es mit seinesgleichen sowie mit vielfältigen π‐elektronenreichen Donoren Komplexe bildet. In Kombination mit den elektronischen Eigenschaften führt dieses dichotome Verhalten zur Bildung selbstorganisierter Nanodrähte im Festkörper sowie zu einer Templatwirkung bei der Bildung eines [3]‐ und zweier [2]Rotaxane mit aromatischen Kronenethern (siehe Bild).</P>
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