Containers, molecular

Complexes of transition metals with macroheterocyclic ligands as host molecules in the construction of molecular containers 98CSR289. 

Electrochemically, the system metal/molten salt is somewhat similar to the system metal/aqueous solution, although there are important differences, arising largely from differences in temperature and in electrical conductivity. Most fused salts are predominantly ionic, but contain a proportion of molecular constituents, while pure water is predominantly molecular, containing very low activities of hydrogen and hydroxyl ions. Since the aqueous system has been extensively studied, it may be instructive to point out some analogues in fused-salt systems. 

Warmuth R The Inner Phase of Molecular Container Compounds As a Novel Reaction Environment J. Inclusion Phenom. Macrocyclic Chem. 2000 37 1-38 Keywords inciusion reaction, photochemistry, photoinduced eiectron transfer, fuiierenes... 

Molecular Containers Design Approaches and Applications D. R. Turner A. Pastor M. Alajarin J. W. Steed... 

Turner DR, Pastor A, Alajarin M, Steed JW (2004) Molecular Containers Design Approaches and Applications 108 97-168... 

The carbonyl complex [Ag(L9)(C0)] (12), also of quite remarkable stability, is obtained by reaction of [Ag(L9)(C2H4)] (11) with CO in hexane. Nevertheless, the CO can be easily removed by increasing the temperature of the solution or by purging with an inert gas. Hence, such a reversible guest encapsulation within a molecular container might find applications for gas separation and storage. Again, one likely reason for the stability of the complexes is the protection offered by the bulky mesityl substituents that surround the ethylene or CO unit. 

The cucurbit [n]uril family (CB[n]) of molecular containers possess remarkable binding affinities and selectivities (Ka values up to 1012M-1, Krei values up to 106) which renders them useful as a component of molecular machines, sensors, and biomimetic systems (123-125). Recently, Wagner and coworkers have reported (126) that CB[10] - with its spacious 870A3 cavity - is capable of acting as a host for free base and metalated tetra (Af-methylpyridinium)porphyrins 19a-d (Fig. 17). Despite the large ellipsoidal deformation of CB[10] upon complexation, the complexed porphyrins retain their fundamental UV/VIS, fluorescence, and electrochemical properties. The CB[ 10] porphyrin... 

R. Warmuth, o-Benzyne Strained Alkyne or Cumu-lene - NMR Characterization in a Molecular Container , Angew. Chem. Int. Ed Engl. 1997, 36,1347-1350. 

Scheme 6.111 Photolysis ofp-tolyldiazirine (552) within the enantiopure molecular container 547d giving rise to the diastereomeric carceplexes 547dO10.

Schmuck, C. (2007) Guest encapsulation within self assembled molecular containers. Angew. Chem., Int. Ed., 46 (31), 5830-5833. 

Immunoglobulins 2-4 150,000-1,000,000 5.5-8.3 Monomers or polymers of four-chain molecular containing two light (MW 20,000) and two heavy (MW 50,000-70,000) chains linked by disulfide bonds... 

While the role of the propan-2-ol in the capsule shown in Figure 10.44 is serendipitous, a number of designer heterocapsules of this type with linkers such as 4,4 bipyridine and 2-aminopyrimidine have been prepared, Figure 10.45.49,50 These kinds of materials, and indeed [4] resorcarenes in general have found significant application as molecular containers, particularly in isolating and protecting... 

MacGillivray, L.R. and Atwood, J.L. (2000) Spherical molecular containers from discovery to design, Adv. Supramol. Chem. 6, 157-183. 

Dynamic covalent chemistry has been used in an atom-efficient self-assembly process to achieve a nearly quantitative one-pot synthesis of a nanoscale molecular container with an inner cavity of approximately 1.7 nm3. 

The subject has been extensively studied by Rebek and coworkers, who have written a substantial number of reviews covering different aspects of the topic [45]. Because of this, we do not intend to describe here in detail the different systems that have been developed, but focus instead on some of the dynamic aspects. Possible applications of these systems include molecular containers, enantioselec-tive receptors, catalysts, drug-delivery devices, separation tools or simply unusual... 

One of the potential uses of any molecular container compound is in the formulation of active pharmaceutical agents. Accordingly, the groups of Kim [29] and Day [30] have demonstrated the ability of CB[7] and CB[8] to modify the properties of Pt-based anticancer agents (Scheme 4.11). For example, Kim s group reported that CB[7] forms a 1 1 complex with oxaliplatin (CB[7] 29). They found that encapsulation of the drug... 

The modulation of the metal-directed self-assembly protocols according to the above-mentioned guidelines introduces additional features for non-covalent molecular containers with respect to their covalent counterparts. Reversibility, selection,... 

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