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Hydrogen-Bond-Driven Controlled Molecular Marriage in Covalent Cages

Acharyya, Koushik and Mukherjee, Partha Sarathi (2014) Hydrogen-Bond-Driven Controlled Molecular Marriage in Covalent Cages. In: CHEMISTRY-A EUROPEAN JOURNAL, 20 (6). pp. 1646-1657.

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Official URL: http://dx.doi.org/10.1002/chem.201303397


A supramolecular approach that uses hydrogen-bonding interaction as a driving force to accomplish exceptional self-sorting in the formation of imine-based covalent organic cages is discussed. Utilizing the dynamic covalent chemistry approach from three geometrically similar dialdehydes (A, B, and D) and the flexible triamine tris(2-aminoethyl)amine (X), three new 3+2] self-assembled nanoscopic organic cages have been synthesized and fully characterized by various techniques. When a complex mixture of the dialdehydes and triamine X was subjected to reaction, it was found that only dialdehyde B (which has OH groups for H-bonding) reacted to form the corresponding cage B3X2 selectively. Surprisingly, the same reaction in the absence of aldehyde B yielded a mixture of products. Theoretical and experimental investigations are in complete agreement that the presence of the hydroxyl moiety adjacent to the aldehyde functionality in B is responsible for the selective formation of cage B3X2 from a complex reaction mixture. This spectacular selection was further analyzed by transforming a nonpreferred (non-hydroxy) cage into a preferred (hydroxy) cage B3X2 by treating the former with aldehyde B. The role of the H-bond in partner selection in a mixture of two dialdehydes and two amines has also been established. Moreover, an example of unconventional imine bond metathesis in organic cage-to-cage transformation is reported.

Item Type: Journal Article
Additional Information: Copyright for this article belongs to the WILEY-V C H VERLAG GMBH, BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY
Keywords: aldehydes; cage compounds; hydrogen bonds; metathesis; self-sorting
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 25 Jul 2014 04:38
Last Modified: 25 Jul 2014 04:38
URI: http://eprints.iisc.ac.in/id/eprint/49519

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