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Macrocyclic Ligands - Web del Profesor

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4 MACROCYCLIC LIGANDS<br />

N<br />

N<br />

2.3.4 Catenands<br />

Me<br />

N OH N<br />

N<br />

OH<br />

Me<br />

(16)<br />

O<br />

O O<br />

O<br />

O<br />

O<br />

O O<br />

O<br />

O<br />

(17)<br />

Catenands (17) are interlocked macrocyclic ligands, which<br />

complex a variety of metal ions. 29<br />

2.4 Polyoxa Macrocycles<br />

Polyoxa macrocycles, known more commonly as the crown<br />

ethers, comprise an extensive area of research, with a repertoire<br />

of types and variations. 30 Some of these macrocycles have<br />

been utilized predominantly for purposes other than metal ion<br />

complexation, and these will not be discussed in depth in this<br />

review. Included in this latter category are the polycarbonyls, 31<br />

polylactones, 32 polylactams 33 and carcerands. 34<br />

2.4.1 Polyether Macrocycles<br />

Polyether macrocycles (18) are the simplest of the polyoxa<br />

macrocycles. The commonly used name for these macrocycles<br />

is the crown ethers, due to their crown-like structure in the<br />

solid state. These molecules have been extensively studied<br />

N<br />

O<br />

O<br />

N<br />

N<br />

O<br />

O<br />

O<br />

O<br />

(18)<br />

as complexing agents for the alkali and alkaline earth metal<br />

ions. 30<br />

2.4.2 Lariat Ethers<br />

The lariat ethers comprise a subset of the polyether<br />

macrocycles, and are identified by their pendant chains. 35<br />

They can be categorized as either N-pivot (19) orC-pivot<br />

(20), depending on which type of atom the chain is attached.<br />

As for their polyether parents, much of the focus on these<br />

macrocycles has been on complexation of alkali and alkaline<br />

earth metal ions.<br />

O<br />

O<br />

O<br />

O<br />

(19)<br />

N<br />

O<br />

2.4.3 Spherands and Hemispherands<br />

O<br />

O<br />

O<br />

O<br />

O<br />

O<br />

(20)<br />

O<br />

O<br />

MeO<br />

These consist of an arrangement of phenyl groups which<br />

provide a preorganized cavity for complexation, 36 e.g. (21)<br />

and (22).<br />

Me Me<br />

Me<br />

Me<br />

OMe<br />

OMe MeO<br />

OMe MeO<br />

OMe<br />

Me<br />

(21)<br />

Me

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