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International audience; Late dinuclear transition-metal (especially group 10 and 11) homoleptic carbonyl complexes are elusive species and have so far not been isolated. A typical example is the 30-electron species [Ni(2)(CO)(5)], the structure and bonding of which is still debated. We show that, by using the AlCp* ligand (isolobal to CO), it is possible to isolate and fully characterize [Ni(2)(AlCp*)(5)] (1), which inspired us to revisit by DFT calculations, the bonding situation within [Ni(2)L(5)] (L = CO, AlCp*) and other isoelectronic species. The short Ni-Ni X-ray distance in 1 (2.270 Å) should not be attributed to the existence of a typical localized triple-bond between the metals, but rather to a strong through-bond interaction involving the three bridging ligands via their donating lone pairs and accepting π* orbitals. In contrast, in the isostructural 32-electron [Au(2)(AlCp*)(5)] (2) cluster an orbital with M-M antibonding and Al...Al bonding character is occupied, which is in accordance with the particularly long Au-Au distance (3.856 Å) and rather short Al...Al contacts between the bridging ligands (2.843 Å). This work shows that, unlike late transition-metal [M(2)(CO)(x)] species, stable [M(2)(AlCp*)(x)] complexes can be isolated, owing to the subtle differences between CO and AlCp*. We propose a similar approach for rationalizing the bonding in the emblematic 34 electron species [Fe(2)(CO)(9)].

International audience; The development of well-defined atomically precise heteronuclear nanoclusters passivated by protecting ligands is presently a booming area, owing to the fact that doping well-known homonuclear nanostructures allows fine-tuning of their properties. Here, we explore by means of density functional theory calculations the possibility of doping the central gold atom in the classical [Au(13)(dppe)(5)Cl(2)](3+)cluster (1) by Os. Although both [Au(13)(dppe)(5)Cl(2)](3+) and [Os@Au(12)(dppe)(5)Cl(2)] have the same total number of electrons, we show that they are not isoelectronic within the formalism of the superatom model, being respectively an 8- and an 18-electron species. It results that they exhibit similar structures but present significantly different optical behaviors (ultraviolet/visible and circular dichroism). Similar results are obtained for the Ru and Fe relatives. Emission properties indicate some redshift of the T(1)→S(1) decay with respect to [Au(13)(dppe)(5)Cl(2)](3+), involving an equatorial distortion of the Au(12)Cl(2) core in the T(1) state, rather than the axial distortion afforded by 1. The sizable highest occupied molecular orbital-lowest unoccupied molecular orbital gaps found for the three doped species suggest that further experimental exploration of different stable doped species derived from the ligand-protected Au(12)Cl(2) core should be encouraged.

International audience

The isoelectronic M7 clusters [Cu3Zn4](Cp*)5 and {[Cu2Zn5](Cp*)5}+ were isolated as unique species pushing the boundaries of the Wade–Mingos rules., The isoelectronic M7 clusters [Cu3Zn4](Cp*)5 (1) and {[Cu2Zn5](Cp*)5}+ (2) are described. While 1 can be isolated only as a minor side product from the reaction of Cu(CH3CO2) with equimolar amounts of [Zn2Cp*2] with the trigonal cluster [CuZn2](Cp*)3 as the major product, 2 is available in acceptable yields from the reaction of [CuZn2](Cp*)3 with the Cp*Zn2-transfer-reagent [Cp*Zn2(Et2O)3][BAr4F]. The trigonal bipyramidal Cu/Zn-clusters exhibit exceptional bonding situations: with formally only one skeleton electron pair they can be regarded as highly electron deficient. However, a detailed DFT analysis reveals that the cluster bonding is supported by 3d orbital contributions of the trigonal metal base unit. The data contribute to the development of an advanced tool-box for synthesis of Hume-Rothery intermetallic (e.g. brass) inspired clusters.

International audience; Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Herein, this work describes the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu H {S P(OnPr) } ] (1 ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1 reveals an unprecedented central Cu hollow icosahedron. Six faces of this icosahedron are capped by Cu triangles, the whole Cu core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S symmetry. The locations of the 18 hydrides in 1 were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ -H, interstitial μ -H (seesaw) and μ -H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the H NMR spectrum of 1 are in line with their coordination environment in the solid state, retaining the S symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu H {Se P(OR) } ] (2 : R=iPr 3 : R=iBu) were synthesized from their sulfur relative 1 via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1 -3 . In addition, the reaction of 1 with [Pd(PPh ) Cl ] in the presence of terminal alkynes led to the formation of new bimetallic Cu-Pd alloy clusters [PdCu H {S P(OnPr) } (C≡CR) ] (4: R=Ph; 5: R=C H F).

Cuboctahedral copper clusters containing a twelve-coordinated main group element (Cl, Br, S) at the center have been synthesized and characterized., We have synthesized and structurally characterized a series of centred cuboctahedral copper clusters, namely [Cu13{S2CNR2}6{C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 CR′}4](PF6), 1a–d (where a: R = nBu, R′ = CO2Me; b: R = nBu, R′ = CO2Et; c: R = iPr, R′ = CO2Et; d: R = nPr, R′ = 3,5-(CF3)2C6H3); [Cu12(μ12-S){S2CNR2}6{C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 CR′}4], 2a–c; [Cu12(μ12-Cl){S2CNR2}6{C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 CR′}4](PF6), 3a–e (where e: R = nBu, R′ = Ph); [Cu12(μ12-Br){S2CNnBu2}6{C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 CPh}4](PF6), 4e; and [Cu12(μ12-Cl)(μ3-Cl){S2CNnBu2}6{C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 CCO2Me}3]+5a. Cluster 1a is the first structurally characterized copper cluster having a Cu13 centered cuboctahedral arrangement, a miniature of the bulk copper fcc structure. Furthermore, the partial Cu(0) character in the 2-electron superatoms 1 was confirmed by XANES. Inverse coordination clusters 2–5 are the first examples of copper clusters containing main group elements (Cl, Br, S) with a hyper-coordination number, twelve. A combined theoretical and experimental study was performed, which shows that the central copper (formally Cu1–) in nanoclusters 1 can be replaced by chalcogen/halogen atoms, resulting in the formation of clusters 2–5 which show enhanced luminescence properties and increase in the ionic component of the host–guest interaction as Br ≈ Cl > S > Cu, which is consistent with the Cu–X Wiberg indices. The new compounds have been characterized by ESI-MS, 1H, 13C NMR, IR, UV-visible, emission spectroscopy, and the structures 2a–b, 3d–e, 4e and 5a were established by X-ray diffraction analysis.

Three bimetallic platinum/silver nanoclusters, PtAg

International audience; Exploring the versatility of atomically precise clusters is a relevant issue in the design of functional nanostructures. Superatomic clusters offer an ideal framework to gain further understanding of the different distinctive size-dependent physical and chemical properties. Here, we propose [Au (SR) ] as a minimal 8-electron superatom related to the prototypical [Au (SR) ] cluster, depicting half of its core-mass (2.3 kDa vs 5.0 kDa). The [Au (SMe) ] cluster fulfills a 1S 1P electronic configuration, with a distorted tetrahedral Au core further viewed as an SP -hybridized superatom. The distinctive optical properties show a blue-shift for the first relevant 1P→1D transition, in comparison to [Au (SR) ] . In addition, chiroptical activity is observed, denoting intrinsic core chirality. We expect that our results can shed light into the variation of the molecular properties according to the size-dependent properties, and serve as guidelines for further experimental exploration of minimal or ultrasmall nanoclusters.

International audience; The first structurally characterized copper cluster with a Cu centered cuboctahedral arrangement, a model of the bulk copper fcc structure, was observed in [Cu (S CN Bu ) (C≡CR) ](PF ) (R=C(O)OMe, C H F) nanoclusters. Four of the eight triangular faces of the cuboctahedron are capped by acetylide groups in μ fashion, and each of the six square faces is bridged by a dithiolate ligand in μ ,μ fashion, which leads to a truncated tetrahedron of twelve sulfur atoms. DFT calculations are fully consistent with the description of these Cu clusters as two-electron superatoms, that is, a [Cu ] core passivated by ten monoanionic ligands, with an a HOMO containing two 1S jellium electrons.

International audience; The first example of ligand protected Cu-Zn clusters is described. Reaction of [CpCu(CN(t)Bu)] with [Zn2Cp*2] yields [(CuCN(t)Bu)4(ZnCp*)4] (1a) and [(CuCN(t)Bu)4(ZnCp*)3(ZnCp)] (1b). According to DFT calculations, the [Cu4Zn4] unit fulfils the unified superatom model for cluster valence shell closing.

International audience

International audience; AlnLn0/2- (n = 4-7, 12), AlnLn+2 (n = 4-7), and Al4L8 clusters were investigated by using the global-search-algorithm-for-minima approach and DFT calculations at the BP86/LANL2DZ level of theory. These investigations indicate that most of the computed species are viable and diamagnetic, although there is no clear general relationship between their shapes and their electron counts. Al4H8 and Al4Cl8 appear to be the most stable compounds in the investigated series.

International audience; In addition to (η5-C5Me5W)2B5H9, (η5-C5Me5W)3(μ-H)B8H8, and (η5-C5Me5W)2B7H9 reported earlier, thermolysis of {η5-C5Me5W}H3B4H8 (1) with BH3*THF leads to the formation of bicapped closo-{η5-C5Me5W}2B6H10 (2) in parallel with a B−B linked dimer of {η5-C5Me5W}2B5H9 (4) and bis-{(η5-C5Me5W)2B5H8}2 (3). Reaction of 4 with a 3-fold excess of Fe2(CO)9 in hexane generates an iron analogue of 2, (η5-C5Me5W)2B5H9Fe(CO)3 (5) in 46% yield. All the metallaboranes, 2, 3, and 5, have been characterized by 1H, 11B NMR spectra and crystal structure determinations. The structures of 2 and 5 appear to follow the regular electron counting rules as they possess seven skeletal electron pairs (sep) appropriate for bicapped octahedral structures. However, their electronic structures revealed by a molecular orbital analysis is more closely related to that of [{η5-C5Me5Re}2B7H7], a cluster that does not obey the classical electron counting rules. Clusters 2 and 5 are notable examples of closo clusters containing four bridging hydrogens. 3 is a coupled-cage structure in which two bicapped trigonal bipyramidal frameworks, W2B5, are joined by an exopolyhedral boron−boron bond.

International audience; The novel cluster anion [Co11Te5(CO)15]- ([3]-) has been isolated and structurally characterized as part of the salt [Cp*2Nb(CO)2][3] (Cp* = C5Me5). The cobalt-centered Co10 pentagonal prism is surrounded by a shell of two μ5-Te, three μ4-Te ligands, and 15 CO groups in terminal, symmetrical, and σ-semibridging bonding modes. The hybrid carbonyl-telluride character of the ligand shell is reflected in the solid state by a one-dimensional assembly of polyhedral prisms along a backbone of [Cp*2Nb(CO)2]+ cations. Electrochemical studies reveal the presence of four redox couples of [3]n (n = −1 to −5). The electronic structures of various metal-centered and empty pentagonal-prismatic (PP) M10 clusters (M = Co, Ni) are calculated and compared to those of pentagonal-antiprismatic (PA) M10 structures. Closed-shells of 152 and 156 metal valence electrons, respectively, are found to determine the electronic structures and chemical properties of these geometries. From these considerations, magnetic properties have been predicted. They have been verified for the [Co11Te7(CO)10]- cluster anion, which exhibits a singlet−triplet gap of 0.318 kcal/mol.

International audience; Analysis of the electronic structure of the electron-deficient cluster cation [Ru4(C6H6)4H4]2+ (12+) by density functional theory calculations shows a very small energy gap (0.06 eV) between the diamagnetic singlet state and the paramagnetic triplet state, as a consequence of the absence of a significant Jahn-Teller distortion in the molecular structure of 12+. Magnetic measurements of [1]Cl2, [1][BF4]2, and [1][PF6]2 show 12+ to be diamagnetic in the fundamental state, with some weak temperature-independent paramagnetism, depending upon the nature of the counterion.

International audience; The electrochemical reduction of [Mo2Cp2(CO)4_μ-η2:η 3-HC≡C-C(R1)(R2)_]+ complexes has been investigated by cyclic voltammetry, controlled-potential electrolysis, and coulometry. On the cyclic voltammetry time scale, the complexes with R1 = H, R2 = H (1+), Me (2+), Et (3+) undergo an irreversible or a quasi-reversible one-electron reduction whereas the analogues with R1 = H, R2 = Fc (4+) and R1 = Me, R2 = Me (5+) and Ph (6+) reduce in a single-step, reversible or quasi-reversible, two-electron process. Two different chemical reactions are involved in the overall reduction mechanism. The first chemical step is assigned as a structural rearrangement, responsible for slowing down the heterogeneous electron transfer. Extended Huckel MO calculations indicate that in the case of the complexes with R1 = H, R2 = Fc and R1 = Me, R2 = Me or Ph, a small increase in the distance between one metal center and the carbon of the C(R1)(R2) group could trigger the two-electron transfer process. The second chemical reaction leading to the final product(s) of the reduction involves radical species, even when a two-electron transfer is observed by cyclic voltammetry. The final products formed in these processes have been identified either by 1H NMR spectroscopy of the compounds extracted from the catholyte after controlled-potential electrolyses or from a comparison of their characteristic redox potentials with those of authentic samples. The nature of the final product(s), either a dimer or μ-alkyne and μ-enyne complexes, is also dependent on the nature of R1 and R2.

A conceptual link between Hume-Rothery inspired complexes/clusters and solid-state intermetallic catalysts with special emphasis on the heterogeneous semi hydrogenation of alkynes is presented. Quantum chemical calculations on the DFT level of theory reveal that [Ni(M'R)n(UHC)4-n] (M’ = Al, Ga, Zn, R = Cp*/Me, UHC = unsaturated hydrocarbons) complexes represent potential molecular models for substrate binding on related intermetallic surfaces. Furthermore, synthetic approaches towards such compounds are presented. In der vorliegenden Arbeit wird ein konzeptueller Vergleich zwischen molekularen Hume-Rothery inspirierten Komplexen/Clustern und intermetallischen Festphasen-Katalysatoren vorgestellt. Dabei wird das Hauptaugenmerk auf die katalytische Semihydrierung von Alkinen gelegt. Quantenchemische Rechnungen auf dem DFT-Level weisen darauf hin, dass Komplexe mit der allgemeinen Formel [Ni(M'R)n(UHC)4-n] (M’ = Al, Ga, Zn, R = Cp*/Me, UHC = ungesättigte Kohlenwasserstoffe) potentielle molekulare Modelle für Substrat-Katalysator Wechselwirkungen darstellen. Außerdem werden synthetische Ansätze zu solchen Komplexen präsentiert.

The wet-chemical, bottom-up synthetic access towards atom-precise Hume-Rothery phase-inspired transition metal/group 13 clusters [MaEb](Cp*)c with Cu/Al, Au/Al, Co/Ga and Ni/Ga combinations was explored, based on the coordination chemistry of the ECp* ligand (E = Al, Ga; Cp* = pentamethylcyclopentadienyl). Focus was laid on the elucidation of repetitive patterns in their formation which can be merged into more generally applicable concepts. Im Rahmen dieser Arbeit wird die nasschemische, "bottom-up" Synthese atompräziser, Hume-Rothery Phasen-inspirierter Übergangsmetall-/Gruppe 13 Cluster [MaEb](Cp*)c mit Cu/Al, Au/Al, Co/Ga und Ni/Ga Kombinationen, aufbauend auf der Koordinationschemie des ECp* Liganden (E = Al, Ga; Cp* = pentamethylcyclopentadienyl) untersucht. Besonderes Augenmerk gilt hierbei der Identifizierung wiederkehrender Muster in deren Bildung, und der Vereinigung ebendieser zu allgemeingültigen Konzepten.

International audience; The stability of large ligated copper(I) clusters of undeca- and dodecanuclearity encapsulating iodide and stabilized by dithio- and diseleno-phosph(in)ates was investigated by density functional theory (DFT) calculations. A bonding analysis is provided, which shows strong iono-covalent bonding between the iodide and its host. The electronic structures of the title compounds suggest the possibility for interesting photoluminescent properties, which were fully investigated by time-dependent DFT calculations including vibronic contributions to simulate the phosphorescence spectra. The quantum mechanical results were compared to the experimental data obtained for the new clusters [Cu11(μ9-I)(μ3-I)3{Se2P(OiPr)2}6]+ and [Cu11(μ9-I)(μ3-I)3(Se2PPh2)6]+, whose syntheses, X-ray structures, and full characterizations are reported in this paper. From this combined theoretical/experimental investigation, it is suggested that the encapsulation by the same copper(I) cages of a formally Cu- anion is also possible. DFT calculations on these species are consistent with the existence of stable two-electron superatoms.

Dendrimers and polymers containing transition metals such as iron, cobalt andrhodium can serve in the fabrication of useful nanomaterials for catalysis, molecularrecognition and molecular electronics. For their construction, ionic bonds, clickchemistry: CuAAC and hydroamination, ROMP and radical polymerization were usedand allowed the formation of new types of metallocenyl polyélectrolytes. Thesynthesis of new gold, silver and palladium nanoparticles from these metallopolymersand metallodendrimers has been developed, leading to specific and well-definedarchitectures. These supramolecular assemblies and molecular engineering opensthe way towards the application of organometallic chemistry in the design of newstructured nanoparticle-containing nanomaterials using the redox properties ofmetallomacromolecules.; Les dendrimères et polymères contenant des métaux de transition comme le fer, lecobalt et le rhodium peuvent servir à la fabrication des nanomatériaux utiles à lacatalyse, la reconnaissance moléculaire et l’électronique moléculaire. Pour leurconstruction, des liaisons ioniques, de la chimie click : CuAAC et hydroamination, lapolymérisation ROMP et la polymérisation radicalaire ont été utilisés et ont permis laformation de nouveaux types de polyélectrolytes metallocéniques. La synthèse denouvelles nanoparticules d’or, d’argent et de palladium à partir de cesmétallopolymères et métallodendrimères ont été mises au point, conduisant à desréseaux à architecture spécifique bien définie. Ces assemblages supramoléculaireset ingénierie moléculaire ouvrent la voie vers l’application de la chimieorganométallique dans la conception de nouveaux nanomatériaux nanoparticulairesstructurés à l’aide des propriétés rédox des métallomacromolécules.

This thesis concerns the synthesis by “click” CuAAC reactions of newnanomaterials that have various applications, in particular in catalysis. Thesemacromolecules are dendrimers, supported dendrimers and polymers that contain1,2,3-triazole rings and were used in the stabilization of essentially palladiumnanoparticles (PdNPs). These PdNPs are extremely active in the catalysis in greensolvents of C-C coupling, reduction of 4-nitrophenol and selective oxidation ofalcohols. The use of these nanoparticle catalysts at the ppm level shows theirefficiency and their ecological aspect. The integration of biferrocene units in thepolymers allowed expanding their applications to electrochemical sensors, reductantsof metallic ions to nanoparticles, polyelectrolytes, polyelectrochromic, and mixedvalentcomplexes. The impregnation of PdNPs stabilized by dendrimers on magneticsupport led to the increase of the catalyst robustness and recyclability using amagnet.; Cette thèse concerne l’élaboration par réaction “click” CuAAC denouveaux nanomatériaux présentant diverses applications, en particulier en catalyse.Ces macromolécules (dendrimères, dendrimères supportés sur oxide et polymères)comprenant des cycles 1,2,3-triazoles ont été utilisés pour stabiliser desnanoparticules essentiellement de palladium actives en catalyse de couplage C-C,réduction du 4-nitrophenol et oxydation des alcools dans des solvants aqueux.L’utilisation de ces nanoparticules à l’échelle du ppm traduit leur efficacité et l’aspectécologique visé avec ce projet. L’intégration d’unités triazolylbiferrocéniques au seinde ces polymères a permis d’étendre la gamme d’applications de ces matériaux auxsondes électrochimiques, réduction d’ions métalliques en nanoparticules, composéspoly-électrolytes, poly-électrochromes, à valence mixte. L’imprégnation denanoparticules de palladium stabilisées par des dendrimères sur support magnétiquea permis d’augmenter la robustesse des catalyseurs ainsi que leur recyclablité paraimantation.