Tri- and nonaferrocenyl thiol dendrons have been synthesized and used to assemble dendronized gold nanoparticles either by the ligand-substitution method from dodecanethiolate-gold nanoparticles (AB(3) units) or Brust-type direct synthesis from a 1:1 mixture of dodecanethiol and dendronized thiol (AB(9) units). The dendronized colloids are a new type of dendrimers with a gold colloidal core. Two colloids containing a nonasilylferrocenyl dendron have been made; they bear respectively 180 and 360 ferrocenyl units at the periphery. These colloids selectively recognize the anions H(2)PO(4)(-) and adenosine-5'-triphosphate (ATP(2)(-)) with a positive dendritic effect and can be used to titrate these anions because of the shift of the CV wave even in the presence of other anions such as Cl(-) and HSO(4)(-). Recognition is monitored by the appearance of a new wave at a less positive potential in cyclic voltammetry (CV). The anion HSO(4)(-) is also recognized and titrated by the dendronized colloid containing the tris-amidoferrocenyl units, because of the progressive shift of the CV wave until the equivalence point. These dendronized colloids can form robust modified electrodes by dipping the naked Pt electrode into a CH(2)Cl(2) solution containing the colloids. The robustness is all the better as the dendron is larger. These modified electrodes can recognize H(2)PO(4)(-), ATP(2)(-) and HSO(4)(-), be washed with minimal loss of adsorbed colloid, and be reused.

Mastering the manipulation of chirality at the nanoscale has long been a priority for chemists, physicists, and materials scientists, given its importance in the biochemical processes of the natural world and in the development of novel technologies. In this vein, the formation of novel metamaterials and sensing platforms resulting from the synergic combination of chirality and plasmonics has opened new avenues in nano-optics. Recently, the implementation of chiral plasmonic nanostructures in photocatalysis has been proposed theoretically as a means to drive polarization-dependent photochemistry. In the present work, we demonstrate that the use of inorganic nanometric chiral templates for the controlled assembly of Au and TiO 2 nanoparticles leads to the formation of plasmon-based photocatalysts with polarization-dependent reactivity. The formation of plasmonic assemblies with chiroptical activities induces the asymmetric formation of hot electrons and holes generated via electromagnetic excitation, opening the door to novel photocatalytic and optoelectronic features. More precisely, we demonstrate that the reaction yield can be improved when the helicity of the circularly polarized light used to activate the plasmonic component matches the handedness of the chiral substrate. Our approach may enable new applications in the fields of chirality and photocatalysis, particularly toward plasmon-induced chiral photochemistry.

The ferrocenylsilylation of the phenol triallyl dendron 2, of the phenol nonaallyl dendron 4, and of the 9-, 27-, 81-, and 243-allyl dendrimers 7-10 (monitored by the disappearance of the signals of the olefinic protons in 1H NMR spectra) has been achieved using ferrocenyldimethylsilane 1 and Karstedt's catalyst in diethyl ether at 40 degrees C, yielding the corresponding ferrocenyl dendrons and dendrimers. An alternative convergent synthesis of the nonaferrocenyl dendron 5 was carried out by reaction of the triferrocenyl dendron 2 with a protected triododendron followed by deprotection. Reaction of the nonaferrocenyl dendron 5 with hexakis(bromomethyl)benzene gave the 54-ferrocenyl dendron 6. All the ferrocenyl dendron and dendrimers produce a chemically and electrochemically reversible ferrocenyl oxidation wave at seemingly the same potential. Stable platinum electrodes modified with the high ferrocenyl dendrimers were fabricated. The soluble orange-red ferrocenyl dendrimers can also be oxidized in CH2Cl2 by [NO][PF6] to the insoluble deep blue polyferrocenium dendrimers. For instance, the 243-ferrocenium dendrimer has been characterized by its Mossbauer spectrum, which is of the same type as that of ferrocenium itself. The ferrocenium dendrimers can be reduced without any decomposition back to the ferrocenyl dendrimer, indicating that these multielectronic redoxstable dendrimers behave as molecular batteries.

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Gold nanoparticles have been functionalized with thiol dendrons containing three redox active amidoferrocenyl or silylferrocenyl units; using cyclic voltammetry, these dendronized gold nanoparticles recognize H2PO4-.

Regenerable and reusable dendritic catalysts have been synthesized by the ionic assembly of polyammonium dendrimers and polyoxometalate (POM) trianionic units. These dendrimers (see example depicted, in which the POM is [PO4{WO(O2)2}4]3−) are found to catalyze, at ambient temperature, the quantitative epoxidation of olefins by H2O2 in water/CDCl3 and the selective and quantitative oxidation of thioanisole to its sulfone.

Enantiopure dendritic polyoxometalate frameworks were prepared by assembling chiral dendritic amines and acidic POM units. The solution CD, UV/Vis and vibrational CD investigations, and the efficiency of these hybrids in the asymmetric oxidation of thioanisole to sulfoxide (14 % ee), indicate significant induced optical activity in the POM cluster. Despite the modest ee, the present reaction confirms a chirality transfer to the POM unit

Metallodendritic catalysts combine the advantages of homogeneous and heterogeneous catalysts: they are soluble and perfectly well defined on the molecular level, and yet they can be recovered by precipitation, ultra-filtration or ultra-centrifugation (as biomolecules) and recycled several times. In this article, we summarize our recent work in this field with examples operating under ambient conditions in metathesis, Pd-catalyzed Sonogashira coupling, redox catalysis of nitrate and nitrite cathodic reduction to ammonia and various oxidation reactions by H 2 O 2 catalyzed by polyoxometallates. The dendritic effects on the catalytic efficiencies are scrutinized, i.e., the comparison of the metallodentritic catalysts with their monomeric models and among the dendrimer generations. It is concluded that metallostars or low-generation metallodendrimers usually are optimized catalysts in terms of efficiency and recovery/re-use.