This chapter describes composite materials composed of dendrimers and metals or semiconductors. Three types of dendrimer/metal-ion composites are discussed: dendrimers containing structural metal ions, nonstructural exterior metal ions, and nonstructural interior metal ions. Nonstructural interior metal ions can be reduced to yield dendrimer-encapsulated metal and semiconductor nanoparticles. These materials are the principal focus of this chapter. Poly(amidoamine) (PAMAM) and poly(propylene imine) dendrimers, which are the two commercially available families of dendrimers, are in many cases monodisperse in size. Accordingly, they have a generation-dependent number of interior tertiary amines. These are able to complex a range of metal ions including Cu 2+ , Pd 2+ , and Pt 2+ . The maximum number of metal ions that can be sorbed within the dendrimer interior depends on the metal ion, the dendrimer type, and the dendrimer generation. For example, a generation six PAMAM dendrimer can contain up to 64 Cu 2+ ions. Nonstructural interior ions can be chemically reduced to yield dendrimer-encapsulated metal nanoparticles. Because each dendrimer contains a specific number of ions, the resulting metal nanoparticles are in many cases of nearly monodisperse size. Nanoparticles within dendrimers are stabilized by the dendrimer framework; that is, the dendrimer first acts as a molecular template to prepare the metal nanoparticles and then as a stabilizer to prevent agglomeration. These composites are useful for a range of catalytic applications including hydrogenations and Heck chemistry. The unique properties of the interior dendrimer microenvironment can result in formation of products not observed in the absence of the dendrimer. Moreover the exterior dendrimer branches act as a selective gate that controls access to the interior nanoparticle, which results in selective catalysis. In addition to single-metal nanoparticles, it is also possible to prepare bimetallic nanoclusters and dendrimer-encapsulated semiconductor nanoparticles, such as CdS, using this same general approach.

The recent emergence of advanced technological applications for colloidal gold suspensions and related particle assemblies and interfaces has created a demand for new chemical and physical techniques with which to characterize them. For macroscopic samples/interfaces, coherent second harmonic generation (SHG) has proven itself a useful characterization tool due, at least in part, to metal-based plasmon enhancement. In an effort to defeat or bypass the size restrictions inherent to SHG, we have utilized a related incoherent methodology, hyper-Rayleigh scattering (HRS), to interrogate aqueous colloidal suspensions of 13 nm diameter gold particles. The nanoscale particles have proven to be remarkably efficient scatterers; when evaluated in terms of the first hyperpolarizability ( ), HRS signals from the gold particles substantially surpass those observable from the best available molecular chromophores. Moreover, the present experiments indicate that is highly sensitive to colloid aggregation and imply that HRS is an effective tool for the characterization of symmetry-reducing perturbations of nanoscale interfaces.The intentional miniaturization of metal/solution interfaces to the point where colloidal stabilization of suspensions of solvated metal particles occurs has been possible, at least at a rudimentary level, for more than a century. Arguably, however, only over the past decade has the concept generated widespread excitement among chemists and materials scientists. Fueling the contemporary interest are demonstrated and emerging applications involving medical screening, 1 chemical sensing, 2 singleelectron conduction (Coulomb blockade behavior), 3 optical frequency tripling, 4 and new materials-assembly schemes. [5][6][7] Accompanying the new applications chemistry is a need for interface characterization. Among the more attractive methodologies for macroscopic metal/solution interface characterization is optical second harmonic generation (SHG). 8 For otherwise centrosymmetric metal structures, interface formation creates an asymmetry providing for interface localized signal generation. SHG has been utilized to interrogate surface symmetry, 9,10 surface charge, 11 adsorbate coverage, 12 and/or adsorbate orientation 13 on gold surfaces as well as to interrogate gold particles at the liquid/air interface. 14 However, the coherent nature of conventional SHG and the necessity of utilizing a finite wavelength of radiation place a practical lower limit on sample size. 15 On the other hand, implementation of incoherent second harmonic generation or hyper-Rayleigh scattering (HRS) methods 16 should circumvent the interface size limitation (albeit at the expense of much smaller signal intensity). 17,18 On the basis of a successful application of HRS to nanoscale silica/water interfaces (surface acidity characterization) 19 and on the basis of a brief report of HRS from silver colloid samples (molecular adsorption effects), 20 we reasoned that the methodology might be applicable to nanoscale gold/water interfaces...

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Photochemical quartz crystal microbalance (PQCM) studies of nanocrystalline titanium dioxide films show evidence of charge-compensating cation intercalation during photolytically induced accumulation layer formation. The manifestation and magnitude of mass uptake (intercalation) are dependent, respectively, on the illumination and intensity of illumination provided. Isotope experiments performed in H 2 O and D 2 O unambiguously identify the cations as protons and deuterons. The experiments extend earlier experiments with dark TiO 2 (and other metal oxide semiconductors) that have implicated cation intercalation as the primary process involved in charge compensation under accumulation conditions.

Electrochemical quartz crystal microbalance (EQCM) measurements provide compelling evidence for chargecompensating cation uptake by nanocrystalline SnO 2 and ZnO electrodes during electron addition. Comparative light water/heavy water measurements establish that the adsorbed or intercalated ions are protons or deuterons. Additional studies as a function of pH implicate water, rather than hydronium ions, as the proton source. The new results, when combined with previous results for titanium dioxide in nonaqueous electrolytes, suggest that charge-compensating cation intercalation is a general mode of reactivity for metal oxide semiconductors. Finally, the new observations raise significant fundamental questions concerning (1) chemical control of band energetics, (2) possible band-edge-unpinning phenomena, and (3) relationships between band edge energies and driving forces for isolated electron transfer reactions.

We report the preparation and characterization of viologen-functionalized generation 2, 4, and 6 poly-(amidoamine) (PAMAM) dendrimers. An amidation reaction between the succinimide ester of 1-ethyl-1′-(3-propionic acid)-4,4′-bipyridylium dibromide and the dendrimer primary amines resulted in 13-34% end group functionalization. The water-soluble dendrimers were examined by 1 H NMR, MALDI-TOF MS, and UV-vis spectroscopy to determine the extent of functionalization. UV-vis spectra, obtained following chemical reduction of the viologenated dendrimers, indicated that the viologen radical cations were largely dimerized, which demonstrates the close proximity of the terminal viologens. Dynamic light scattering (DLS) measurements indicate that the oxidized viologenated-dendrimers are predominately unaggregated in aqueous electrolyte solutions. Diffusion coefficients determined by chronoamperometry for the three generations of viologenated PAMAM dendrimer are within 15% of values calculated using the Stokes-Einstein relationship for individual unaggregated dendrimers. Reversible voltammetry was obtained for all three generations of dendrimers for the first viologen reduction wave. The magnitude of the peak or steady-state currents indicated incomplete electrolysis of the dendrimer viologen moieties, whereas the presence of a single wave showed that all electrochemically addressable groups were equivalent. Cycling through the second reduction wave resulted in electrode passivation due to irreversible electroprecipitation. Adsorption of a stable film of oxidized viologenated-dendrimer on a Au electrode is also demonstrated by cyclic voltammetry.

Hyper-Rayleigh scattering (HRS) experiments performed on nanometer-scale SiO2/water interfaces (aqueous colloidal suspensions) display finite, measurable signals. HRS is not constrained by the orientational, size, and/or charge restrictions inherent to conventional interfacial second harmonic generation (SHG) or electric-field-induced SHG measurements. Thus, apparently for the first time, the second-order nonlinear optical (NLO) response of ultrasmall interfaces has been measured. pH- and electrolyte-dependent experiments show the response to be sensitive to changes in chemical composition at the silicon dioxide/solution interface. HRS provides detailed information about the surface of these technologically interesting and important particles in their native solution-phase environment.