Carcerand

 ( Supramolecular Chemistry ) 

In host–guest chemistry, a carcerand () is a host molecule that completely entraps its guest (which can be an ion, atom or other chemical species) so that it will not escape even at high Temperature. Shell closure of two cavitands forms carcerand complexes with components of the medium as permanent guests Donald J. Cram, Stefan Karbach, Young Hwan Kim, Lubomir Baczynskyj, Gregory W. KallemeynJ. Am. Chem. Soc.; 1985; 107(8); 2575-2576. This type of molecule was first described in 1985 by Donald J. Cram and coworkers. The complexes formed by a carcerand with permanently imprisoned guests are called .

In contrast, hemicarcerands allow guests to enter and exit the cavity at high temperatures but will form stable complexes at ambient temperatures. Recent Highlights in Hemicarcerand Chemistry Ralf Warmuth and Juyoung Yoon, Accounts of Chemical Research Volume 4, Issue 2, Pages 95-105, 2001. The complexes formed by a hemicarcerand and a guest are called hemicarceplexes.

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Reactivity of bound guests Cram described the interior of the container compound as the inner phase in which radically different reactivity was observed. The Inner Phase of Molecular Container Compounds as a Novel Reaction Environment Ralf Warmuth Journal of Inclusion Phenomena and Macrocyclic Chemistry 37: 1–38, 2000. He used a hemicarcerand to isolate highly unstable, antiaromatic cyclobutadiene at room temperature. The hemicarcerand stabilizes guests within its cavity by preventing their reaction with other molecules.

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Synthesis The first generation carcerands are based on calixarene hemicarcerands with 4 alkyl substituents on the upper rim and 4 reactive on the lower rim. The coupling of both hemicarcerands takes place through a spacer group. In the original 1985 publication two different hemicarcerands react, one with chloromethylene reactive groups and one with thiomethylene reactive groups in a nucleophilic displacement and the resulting spacer group is a dimethylsulfide (CH₂SCH₂). In this experiment the guests were the molecules already present in the reaction medium such as argon and dimethylformamide.

In another configuration the 4 lower rim functional groups are which condense with O-Phenylenediamine to the corresponding di-imines. The 4 spacer groups connecting the two spheres are now much longer and consequently the internal cavity is much larger. Compounds trapped in the cavity are said to be held there by constrictive binding. Constrictive binding of large guests by a hemicarcerand containing four portals Mimi L. C. Quan, Donald J. Cram J. Am. Chem. Soc.; 1991; 113(7); 2754-2755. They can be introduced by simply heating in neat solvent like hexachlorobutadiene (a fungicide). The half-life of the reverse process is 3.2 hours at 25 °C in CDCl₃ by NMR analysis. Ferrocene can be introduced by heating with the hemicarcerand in a large bulky solvent such as tripiperidylphosphine oxide. The half-life for ferrocene liberation is 19.6 hours at 112 °C.

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Large carcerands The internal cavity of a carcerand can be as large as 1700 angstrom³ (1.7 nanometer³) when six hemicarcerands form a single octahedral compound. One-Pot, 18-Component Synthesis of an Octahedral Nanocontainer Molecule Xuejun Liu, Yong Liu, Gina Li, Ralf Warmuth, Angewandte Chemie International Edition Volume 45, Issue 6, Pages 901–904, 2006. This is accomplished by dynamic covalent chemistry in a one-pot condensation of 6 equivalents of a and 12 equivalents of ethylene diamine with trifluoroacetic acid catalyst in chloroform at room temperature followed by reduction of the imine bonds with sodium borohydride.

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