Dendrimers, ferrocene-based

The electrochemical behavior of ferrocene-based polymers [15] and of complexes containing a large, well defined number of ferrocene-type units [16] had already been reported when several groups became interested in dendrimer research. In the past few years several dendrimers of different chemical nature and structure carrying ferrocene-type units in the periphery have been synthesized... 

Ferrocene-based Branched Polymers (Dendrimers). One of the topics in macromolecular chemistry is constituted by dendrimers, or hyperbranched macromolecules of tridimensional globular structure, the surface of which is characterized by a large number of functional groups, Scheme 4. Such functionalities impart to the molecules solubility, viscosity and thermal properties different from those of the common linear polymers.38c,d 44... 

Organometallic chemistry, in particular the chemistry of ferrocenes, is affording significant contributions to the field. As illustrated in Figure 28, ferrocene-based dendrimers can assume compositions ranging from a single ferrocene unit properly functionalized45 to multiferrocene units placed in the outer zone of the surface.46... 

Figure 28 A schematic representation of the possible composition of ferrocene-based dendrimers. (a) Dendrimers containing a single ferrocene unit (b) dendrimers containing multiple ferrocene units...

The same reasons for the interest in incorporating ferrocene units into polymers also provided motivation for the synthesis of dendritic macromolecules of well-defined size and structure containing ferrocenyl units. An important additional rationale for the construction of ferrocenyl dendrimers is provided by the fact that such macromolecules raise the possibility of combining the unique and valuable redox properties associated with the ferrocene nucleus with the highly structured macromolecular chemistry. This may provide access to materials of nanoscopic size possessing unusual symmetrical architectures, as well as specific physical and chemical properties which would be expected to differ from those of the ferrocene-based materials prepared to date. 

The potential value for the ferrocene-based process exhibits no or only minor dependence on dendrimer generation. 

Cuadrado and coworkers have synthesized and characterized poly(propylenimine) dendrimers modified with neutral ferrocenyl (Fc) groups (diammino butane-dend-(NHCOFc) , n = 4, 8, 16, 32, and 64, for GO, 1, 2, 3, and 4, respectively, Fig. 4b) [76], These dendrimers also showed a ferrocene-based single redox wave at the same potential E " = +0.59, +0.57, +0.59, +0.58, and +0.59 V versus SCE for GO, 1, 2, 3, and 4, respectively) in TBAH/CH2CI2 solution, pointing to the absence of electronic interactions. In addition, the anodic peak appeared to be diffusional, whereas the cathodic peak appeared to be stripping in shape. These results suggested the deposition of dendrimers during oxidation and their abrupt redissolution upon reduction. 

Ferrocenyl-modified dendrimers were found to be able to recognize small inorganic anions [105, 106]. From shifts of the ferrocene-based peak potentials in cyclic voltammetry in CH2CI2 solution and shifts of 5nh in NMR, resulting from the titration of the dendrimers with the tetrabutylammonium salts of anions such as H2P04 , HS04 , C1 , and NO3 , changes in the apparent association constant of the anion with the ferrocenyl dendrimer were monitored. 

The synthesis and properties of star polymers and dendrimers functionalized with ferrocene units has attracted a great deal of attention. The synthesis of high-generation dendrimers functionalized with chiral ferrocenyl units in their structures has been reported. The chiroptical properties of this class of dendrimer was dependent on the number of ferrocenyl groups and their chemical environment, but not on their position within the dendrimer. Deschenaux has reported the synthesis of hquid crystalline ferrocene-based polymers prossessing an enantiotropic smectic A phase. Ferrocene-functionahzed cyclic siloxane (29) and silsesquioxane branched polymers have also been reported. A hyperbranched polymer with a cubic silsesquioxane core was used to mediate the electrocatalytic oxidation of ascorbic acid. 

For longer polymers, adsorption and film formation can take place in organic solvents, which are good solvents for the neutral ferrocene-based species but bad solvents for the oxidized species [153, 154, 160-165]. In this case, even diblock copolymers precipitate on the electrode, without indication of the formation of micellar structures upon electrochemical switching [166-168]. Co-precipitation with carbon nanotubes onto electrodes has been achieved [169]. As a matter of fact, common solvents for both redox states are seldom available, unless the hydrophobic ferrocene units are complexed by cyclodextrins (in this case, water is a good solvent) [170, 171]. As another example, dendritic ferrocene-based polymers are sufficiently solubilized, even after oxidation in organic media (probably, the insoluble units are shielded in the interior of the dendrimers) [172]. Star-like... 

Mesomorphic dendrimers containing electroactive units have potential for construction of dendrimer based molecular switches. Deschenaux et al. reported [154] the synthesis and liquid-crystalline properties of a novel dendrimer containing six mesomorphic ferrocene units. Apart from exhibiting a broad enantiotropic smectic A phase as determined by polarized optical microscopy, DSC, and XRD studies, thermogravimetry revealed the excellent thermal stability of the macromolecule. 

There are, of course, metal-containing dendrimers that belong to more than one of the above-mentioned categories. Examples are the heptametallic dendrimer made of a central Fe(Cp)(C6Me6)+ core and coated with 6 ferrocene moieties [ 12], and the heterometallic dendrimers made of an organic core, containing up to 6 Pt(IV)-based organometallic species in the branches, and coated with up to 12 ferrocene units [13]. 

The electroactive units in the dendrimers that we are going to discuss are the metal-based moieties. An important requirement for any kind of application is the chemical redox reversibility of such moieties. The most common metal complexes able to exhibit a chemically reversible redox behavior are ferrocene and its derivatives and the iron, ruthenium and osmium complexes of polypyridine ligands. Therefore it is not surprising that most of the investigated dendrimers contain such metal-based moieties. In the electrochemical window accessible in the usual solvents (around +2/-2V) ferrocene-type complexes undergo only one redox process, whereas iron, ruthenium and osmium polypyridine complexes undergo a metal-based oxidation process and at least three ligand-based reduction processes. 

Mixed-metal dendrimers containing up to 6 Pt(IV)-based organometallic species in the branches and 12 peripheral ferrocene units (8) have recently been synthesized and their electrochemical behavior investigated [13]. As in the previously discussed examples, multi-electron reversible oxidation processes, assigned to the equivalent, non-interacting ferrocene units, have been observed. The authors point out that cyclic voltammetry is a powerful tool to support the structure of the dendrimers containing ferrocene units. 

Sihcon chemistry also provides a means for preparing dendrimers capped with metal ions [3,65]. For example, ferrocene [78,79], Co +, [80], Ru [81], and [9] have been hnked to the periphery of sihcon-based dendrimers. These materials are prepared by displacing reactive Si-Cl functional groups with any of a variety of nucleophiles, such as amines, alcohols, or Grignard reagents, containing the metal complexes or hgands. 

Ferrocenyl-based polymers are established as useful materials for the modification of electrodes, as electrochemical biosensors, and as nonlinear optical systems. The redox behavior of ferrocene can be tuned by substituent effects and novel properties can result for example, permethylation of the cyclopentadienyl rings lowers the oxidation potential, and the chaige transfer salt of decamethylfer-rocene with tetracyanocthylene, [FeCpJ]" (TCNE], is a ferromagnet below = 4.8 K, and electrode surfaces modified with a pentamethylferrocene derivative have been used as sensors for cytochrome c These diverse properties have provided an added impetus to studies on ferrocene dendrimers. 

Fe2(III,III)2+ states. By considering that organometallic dendrimers based on conjugated ferrocene units are of special importance since mixed-valence states have interesting electrical, redox, and magnetic properties, recently three generations of polypropylene amine) dendrimers, decorated at their periphery with 4, 8, and 16 (compound 6, Fig. 6.6a) BFc units, respectively, have been synthesized and the electrochemical behavior of the dendrimers complexed with (3-cyclodextrins ([3-CD) and adsorbed at self-assembled monolayers (SAMs) of heptathioether-functionalized [3-CD on gold (molecular printboard) has been studied.40... 

Figure 28 Plot of ln(///0) versus (in arbitrary units) for the first, second, and third generation ferrocene dendrimers based on A. The largest compound shows the smallest slope a D. (Reprinted with permission from D. Valentini, M. Pregosin, P. S. Ruegger, H (2000) Organometallics 19 2551. 2000 American Chemical Society)...

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