Amidoferrocenyl dendrimer

The equivalence point was found by CV to correspond to the interaction of one ferrocenyl branch per equiv. anion in this series of dendrimers. The 9- and 18-amidoferrocenyl dendrimers (resp. 9-Fc and 18-Fc) were compared to monomeric (1-Fc) and trinuclear (3-Fc) amidoferrocenyl derivatives (Fig. 2), and, as indicated by the above data, a strongly positive dendritic... 

Scheme 9 Syntheses of 24-amidoferrocenyl dendrimer (24-Fc) that recognizes oxo-anions (left) and cationic 24-p.aminotolueneFeCp dendrimer (24-FeAr) that recognizes chloride and bromide (right)...

The first ferrocenyl dendrimers designed for function were synthesized by reaction of amine-terminated dendrimers with ferrocenoyl chloride, which yielded amidoferrocenyl dendrimers that were redox exo-receptors of oxo-anions [54], It was subsequently found that silylferrocenylation of polyolefin dendrimers yielded polysilylferrocenyl dendrimers (Scheme 8.4). 

It also proved possible to attach aza-crown ethers to the periphery of a POPAM dendrimer via amidoferrocenyl units (Fig. 4.5) [9a] and also to decorate the outer shell of a second-generation POPAM dendrimer alternately with eight F-stilbene and eight 4-tert-bulylbenzenesulphonic acid units [9b]. Various other... 

With the diaminobutane (DAB) dendrimers formulated G -DAB-dend-(NH2) , amidoferrocenyl [34-42] and pentamethyl-amidoferrocenyl [64,65] dendrimers have been synthesized (Scheme 2) for the five generations from Gi (4 branches) to G5 (theoretical number 64 branches). 

Scheme 2 Syntheses of third-generation amidoferrocenyl [34-41] and pentamethylamido-ferrocenyl dendrimers [64,65] from the corresponding DSM polyamine dendrimer G3-dend-(NH2)i6- For analysis and comparison of their behavior as hosts of anions, see [64,65]...

The supramolecular assembly of dendrimers via H-bonding has been accomplished by Astruc, Boisselier, and Ornelas in which commercial dendritic poly(propylenimine) cores are rapidly and reversibly H-bonded to triallyl-or tris-amidoferrocenyl phenol dendrons these novel supramolecular assemblies were used for the electrochemical recognition of H2P04 and adenosine-triphosphate anions. ... 

The amidoferrocenyl or silylferrocenyl monomers do not show any effect, however. Therefore, the dendrimer topology is important for recognition of oxo-anions. The appropriate encapsulation of the anionic host between the dendritic tethers is a key factor that very much increases the interaction between the functional ferrocenyl termini and the guest (Scheme 8.6). 

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