Synthesis, Electrochemistry, and Excited-State Properties of Three Ru(II) Quaterpyridine Complexes.

The complexes [Ru(qpy)LL'](2+) (qpy = 2,2':6',2″:6″,2‴-quaterpyridine), with 1: L = acetonitrile, L'= chloride; 2: L = L'= acetonitrile; and 3: L = L'= vinylpyridine, have been prepared from [Ru(qpy) (Cl)2]. Their absorption spectra in CH3CN exhibit broad metal-to-ligand charge transfer (MLCT) absorptions arising from overlapping (1)A1 → (1)MLCT transitions. Photoluminescence is not observed at room temperature, but all three are weakly emissive in 4:1 ethanol/methanol glasses at 77 K with broad, featureless emissions observed between 600 and 1000 nm consistent with MLCT phosphorescence. Cyclic voltammograms in CH3CN reveal the expected Ru(III/II) redox couples. In 0.1 M trifluoroacetic acid (TFA), 1 and 2 undergo aquation to give [Ru(II)(qpy)(OH2)2](2+), as evidenced by the appearance of waves for the couples [Ru(III)(qpy)(OH2)2](3+)/[Ru(II)(qpy)(OH2)2](2+), [Ru(IV)(qpy)(O)(OH2)](2+)/[Ru(III)(qpy)(OH2)2](3+), and [Ru(VI)(qpy)(O)2](2+)/[Ru(IV)(qpy)(O)(OH2)](2+) in cyclic voltammograms.

Charge-Transfer Effects in Ligand Exchange Reactions of Au25 Monolayer-Protected Clusters.

Reported here are second-order rate constants of associative ligand exchanges of Au25L18 nanoparticles (L = phenylethanethiolate) of various charge states, measured by proton nuclear magnetic resonance at room temperature and below. Differences in second-order rate constants (M(-1) s(-1)) of ligand exchange (positive clusters ∼1.9 × 10(-5) versus negative ones ∼1.2 × 10(-4)) show that electron depletion retards ligand exchange. The ordering of rate constants between the ligands benzeneselenol > 4-bromobenzene thiol > benzenethiol reveals that exchange is accelerated by higher acidity and/or electron donation capability of the incoming ligand. Together, these observations indicate that partial charge transfer occurs between the nanoparticle and ligand during the exchange and that this is a rate-determining effect in the process.

Temperature dependence of solid-state electron exchanges of mixed-valent ferrocenated Au monolayer-protected clusters.

Electron transfers (ETs) in mixed-valent ferrocene/ferrocenium materials are ordinarily facile. In contrast, the presence of ~1:1 mixed-valent ferrocenated thiolates in the organothiolate ligand shells of <2 nm diameter Au225, Au144, and Au25 monolayer-protected clusters (MPCs) exerts a retarding effect on ET between them at and below room temperature. Near room temperature, in dry samples, bimolecular rate constants for ET between organothiolate-ligated MPCs are diminished by the addition of ferrocenated ligands to their ligand shells. At lower temperatures (down to ~77 K), the thermally activated (Arrhenius) ET process dissipates, and the ET rates become temperature-independent. Among the Au225, Au144, and Au25 MPCs, the temperature-independent ET rates fall in the same order as at ambient temperatures: Au225 > Au144 > Au25. The MPC ET activation energy barriers are little changed by the presence of ferrocenated ligands and are primarily determined by the Au nanoparticle core size.

Solution voltammetry of 4 nm magnetite iron oxide nanoparticles.

The voltammetry of solution-dispersed magnetite iron oxide Fe3O4 nanoparticles is described. Their currents are controlled by nanoparticle transport rates, as shown with potential step chronoamperometry and rotated disk voltammetry. In pH 2 citrate buffer with added NaClO4 electrolyte, solution cyclic voltammetry of these nanoparticles (average diameter 4.4 ± 0.9 nm, each containing ca. 30 Fe sites) displays an electrochemically irreversible oxidation with E(PEAK) at ca. +0.52 V and an irreversible reduction with E(PEAK) at ca. +0.2 V vs Ag/AgCl reference electrode. These processes are presumed to correspond to the formal potentials for one-electron oxidation of Fe(II) and reduction of Fe(III) at their different sites in the magnetite nanoparticle structure. The heterogeneous electrode reaction rates of the nanoparticles are very slow, in the 10(-5) cm/s range. The nanoparticles are additionally characterized by a variety of tools, e.g., TEM, UV/vis, and XPS spectroscopies.

Electronic conductivity of films of electroflocculated 2 nm iridium oxide nanoparticles.

The electronic conductivity of films of iridium oxide (IrO(x)) composed of ca. 2 nm nanoparticles (NPs) is strongly dependent on the film oxidation state. The Ir(IV)O(x) NPs can be electrochemically converted to several oxidation states, ranging from Ir(III) to Ir(V) oxides. The NP films exhibit a very high apparent conductivity, e.g., 10(-2) S cm(-1), when the NPs are in the oxidized +4/+5 state. When the film is fully reduced to its Ir(III) state, the apparent conductivity falls to 10(-6) S cm(-1).

Formation of iridium(IV) oxide (IrOX) films by electroflocculation.

Films of iridium(IV) oxide nanoparticles (IrOX NPs) become deposited on electrodes from nanoparticle solutions when potentials sufficient to initiate water oxidation are applied. Evidence is given that the film-forming mechanism is nanoparticle precipitation. Following an induction period during which a significant amount of charge is passed, the NPs begin to deposit as islands. It appears that the proton release that accompanies nanoparticle oxidation triggers the nanoparticle electroflocculation and subsequent precipitation. Flocculation from nanoparticle solutions can also be induced by the addition of a chemical oxidant (Ce(IV)). The film formation is followed by cyclic voltammetry (CV), rotated ring disk voltammetry (RRDE), and electrochemical quartz crystal microbalance (eQCM) measurements, supplemented with AFM and SEM microscopies.

Kinetics and low temperature studies of electron transfers in films of small (<2 nm) Au monolayer protected clusters.

This work examines the temperature dependence of electron transfer (ET) kinetics in solid-state films of mixed-valent states of monodisperse, small (<2 nm) Au monolayer protected clusters (MPCs). The mixed valent MPC films, coated on interdigitated array electrodes, are Au25(SR)18(0/1-), Au25(SR)18(1+/0), and Au144(SR)60(1+/0), where SR = hexanethiolate for Au144 and phenylethanethiolate for Au25. Near room temperature and for ca. 1:1 mol:mol mixed valencies, the bimolecular ET rate constants (assuming a cubic lattice model) are ~2 × 10(6) M(-1) s(-1) for Au25(SR)18(0/1-), ~3 × 10(5) M(-1) s(-1) for Au25(SR)18(1+/0), and ~1 × 10(8) M(-1) s(-1) for Au144(SR)60(1+/0). Their activation energy ET barriers are 0.38, 0.34, and 0.17 eV, respectively. At lowered temperatures (down to ca. 77 K), the thermally activated (Arrhenius) ET process dissipates revealing a tunneling mechanism in which the ET rates are independent of temperature but, among the different MPCs, fall in the same order of ET rate: Au144(+1/0) > Au25(0/1-) > Au25(1+/0).

Synthesis and electrochemistry of 6 nm ferrocenated indium-tin oxide nanoparticles.

Indium-tin oxide (ITO) nanoparticles, 6.1 ± 0.8 nm in diameter, were synthesized using a hot injection method. After reaction with 3-aminopropyldimethylethoxysilane to replace the initial oleylamine and oleic acid capping ligands, the aminated nanoparticles were rendered electroactive by functionalization with ferrocenoyl chloride. The nanoparticle color changed from blue-green to light brown, and the nanoparticles became more soluble in polar solvents, notably acetonitrile. The nanoparticle diffusion coefficient (D = 1.0 × 10(-6) cm(2)/s) and effective ferrocene concentration (C = 0.60 mM) in acetonitrile solutions were determined using ratios of DC and D(1/2)C data measured by microdisk voltammetry and chronoamperometry. The D result compares favorably to an Einstein-Stokes estimate (2.1 × 10(-6) cm(2)/s), assuming an 8 nm hydrodynamic diameter in acetonitrile (6 nm for the ITO core plus 2 nm for the ligand shell). The ferrocene concentration result is lower than anticipated (ca. 1.60 mM) based on a potentiometric titration of the ferrocene sites with Cu(II) in acetonitrile. Cyclic voltammetric data indicate tendency of the ferrocenated nanoparticles to adsorb on the Pt working electrode.

Electron transfer dynamics of iridium oxide nanoparticles attached to electrodes by self-assembled monolayers.

Self-assembled monolayers (SAMs) of carboxylated alkanethiolates (-S(CH(2))(n-1)CO(2)(-)) on flat gold electrode surfaces are used to tether small (ca. 2 nm d.) iridium(IV) oxide nanoparticles (Ir(IV)O(X) NPs) to the electrode. Peak potential separations in cyclic voltammetry (CV) of the nanoparticle Ir(IV/III) wave, in pH 13 aqueous base, increase with n, showing that the Ir(IV/III) apparent electron transfer kinetics of metal oxide sites in the nanoparticles respond to the imposed SAM electron transfer tunneling barrier. Estimated apparent electron transfer rate constants (k(app)(0)) for n = 12 and 16 are 9.8 and 0.12 s(-1). Owing to uncompensated solution resistance, k(app)(0) for n = 8 was too large to measure in the potential sweep experiment. For the cathodic scans, coulometric charges under the Ir(IV/III) voltammetric waves were independent of potential scan rate, suggesting participation of all of the iridium oxide redox sites (ca. 130 per NP) in the NPs. These experiments show that it is possible to control and study electron transfer dynamics of electroactive nanoparticles including, as shown by preliminary experiments, that of the electrocatalysis of water oxidation by iridium oxide nanoparticles.

Mass spectrometry of ligand exchange chelation of the nanoparticle [Au25(SCH2CH2C6H5)18]1- by CH3C6H3(SH)2.

Mass spectrally detected products of ligand exchange reactions of the nanoparticle [Au25(SC2H4C6H5)18](1-), (abbrev. Au25(SC2Ph)18), where the dithiol is toluene-3,4-dithiol, CH3C6H3(SH)2, include nanoparticles containing both doubly (bidentate, or chelating) and singly bonded dithiol. The bidentate binding displaces two of the original -SC2Ph ligands, and singly bonded dithiol displaces one -SC2Ph ligand, while maintaining, for mass spectrally detected species, occupancy of 18 ligation sites. Extended exchange reaction times result in an apparent maximum of six chelated dithiolates. In the Au25(SC2Ph)18 nanoparticle, six semi-rings of -S(R)-Au-S(R)-Au-S(R)- act as the protecting ligand shell surrounding a Au13 core; the chelation is suggested to involve binding of dithiolates to adjacent semi-rings, rather than to a single semi-ring. Both high resolution ESI and lower resolution MALDI spectra support the product assignments. A minor extent of bidentate ligand incorporation is sufficient to severely compromise the well-known Au25(SC2Ph)18 UV-vis fine structure and to alter its voltammetric pattern, reflecting either associated semi-ring distortion and/or decay of the exchange product.

Synthesis of monodisperse [Oct4N(+)][Au25(SR)18(-)] nanoparticles, with some mechanistic observations.

A single phase (THF) synthesis of monodisperse [Oct(4)N(+)][Au(25)(SR)(18)(-)] nanoparticles is described that yields insights into pathways by which it is formed from initially produced larger nanoparticles. Including the Oct(4)N(+)Br(-) salt in a reported single phase synthetic procedure enables production of reduced nanoparticles having a fully occupied HOMO molecular energy level (Au(25)(SR)(18)(-), as opposed to a partially oxidized state, Au(25)(SR)(18)(0)). The revised synthesis accommodates several (but not all) different thiolate ligands. The importance of acidity, bromide, and dioxygen on Au(25) formation was also assessed. The presence of excess acid in the reaction mixture steers the reaction toward making Au(25)(SR)(18); while bromide does not seem to affect Au(25) formation, but it may play a role in maintaining the -1 oxidation state. Conducting the nanoparticle synthesis and "aging" period in the absence of dioxygen (under Ar) does not produce small nanoparticles, providing insights into the pathway of reaction product "aging" in the synthesis solvent, THF. The "aging" process favors the Au(25)(-) moiety as an end point and possibly involves degradation of larger nanoparticles by hydroperoxides formed from THF and oxygen.

An editor's view of analytical chemistry (the Discipline).

The author recounts progress observed in analytical chemistry (the discipline) from the vantage point of a 20-year editor of Analytical Chemistry (the journal). The recounting draws liberally from the journal's monthly editorials. A complete listing of the editorials can be found in Supplemental Material .

The story of a monodisperse gold nanoparticle: Au25L18.

Au nanoparticles (NPs) with protecting organothiolate ligands and core diameters smaller than 2 nm are interesting materials because their size-dependent properties range from metal-like to molecule-like. This Account focuses on the most thoroughly investigated of these NPs, Au(25)L(18). Future advances in nanocluster catalysis and electronic miniaturization and biological applications such as drug delivery will depend on a thorough understanding of nanoscale materials in which molecule-like characteristics appear. This Account tells the story of Au(25)L(18) and its associated synthetic, structural, mass spectrometric, electron transfer, optical spectroscopy, and magnetic resonance results. We also reference other Au NP studies to introduce helpful synthetic and measurement tools. Historically, nanoparticle sizes have been described by their diameters. Recently, researchers have reported actual molecular formulas for very small NPs, which is chemically preferable to solely reporting their size. Au(25)L(18) is a success story in this regard; however, researchers initially mislabeled this NP as Au(28)L(16) and as Au(38)L(24) before correctly identifying it by electrospray-ionization mass spectrometry. Because of its small size, this NP is amenable to theoretical investigations. In addition, Au(25)L(18)'s accessibility in pure form and molecule-like properties make it an attractive research target. The properties of this NP include a large energy gap readily seen in cyclic voltammetry (related to its HOMO-LUMO gap), a UV-vis absorbance spectrum with step-like fine structure, and NIR fluorescence emission. A single crystal structure and theoretical analysis have served as important steps in understanding the chemistry of Au(25)L(18). Researchers have determined the single crystal structure of both its "native" as-prepared form, a [N((CH(2))(7)CH(3))(4)(1+)][Au(25)(SCH(2)CH(2)Ph)(18)(1-)] salt, and of the neutral, oxidized form Au(25)(SCH(2)CH(2)Ph)(18)(0). A density functional theory (DFT) analysis correctly predicted essential elements of the structure. The NP is composed of a centered icosahedral Au(13) core stabilized by six Au(2)(SR)(3) semirings. These semirings present interesting implications regarding other small Au nanoparticle clusters. Many properties of the Au(25) NP result from these semiring structures. This overview of the identification, structure determination, and analytical properties of perhaps the best understood Au nanoparticle provides results that should be useful for further analyses and applications. We also hope that the story of this nanoparticle will be useful to those who teach about nanoparticle science.

Interfacial ion transfers between a monolayer phase of cationic Au nanoparticles and contacting organic solvent.

The highly cationic nanoparticle [Au(225)(TEA-thiolate(+))(22)(SC6Fc)(9)] adsorbs so strongly on Pt electrodes from CH(3)CN/Bu(4)NClO(4) electrolyte solutions that films comprised of 1-2 monolayers of nanoparticles can be transferred to nanoparticle-free electrolyte solutions without desorption and ferrocene voltammetry stably observed. (TEA-thiolate(+) = -S(CH(2))(11)N(CH(2)CH(3))(3)(+); SC6Fc = S(CH(2))(6)-ferrocene; Fc = ferrocene). The Fc(+/0) redox couple's voltammetry is used to detect the adsorption. The apparent formal potential (E(o)'(APP)) of the Fc(+/0) couple depends on the electrolyte--its anion, cation, and concentration--in the contacting nanoparticle-free solution. A 10-fold change in electrolyte concentration shifts the Fc(+/0) E(o)'(APP) by 48-67 mV, depending on the electrolyte. The dependency is interpreted to reflect the energetics of transfer of charge-compensating anions from the electrolyte solution to the monolayer nanoparticle "phase", promoted by the formation of Fc(+) sites in the nanoparticle film. This interpretation is supported by electrochemical quartz crystal microbalance results. Some further aspects of the results suggest adsorption of electrolyte cations at the nanoparticle film/electrolyte solution interface. The interface mimics a liquid/liquid interface between immiscible electrolyte solutions, in which the ion transfer approaches permselective behavior. The experimental results show that even 1-2 monolayers of highly ionic nanoparticles can behave as a polyelectrolyte "phase".

Electrospray ionization mass spectrometry of intrinsically cationized nanoparticles, [Au(144/146)(SC(11)H(22)N(CH(2)CH(3))(3)(+))(x)(S(CH(2))(5)CH(3))(y)](x+).

Electrospray ionization triple-quadrupole mass spectrometry of ca. 1.6 nm diameter thiolate-protected gold nanoparticles has been achieved at higher resolution than in previous reports. The results reveal the presence of nanoparticles with formulas Au(144)L(60) and Au(146)L(59), present in the sample as a mixture. The improved resolution is based on lowering m/z by exchanging multiple [-SC(11)H(22)N(CH(2)CH(3))(3)(+)] ligands into the original [-S(CH(2))(5)CH(3)] ligand shell. The nanoparticles are thus intrinsically cationized and appear as a series of 10+ to 15+ mass spectral peaks. The assigned state of charge was confirmed by a collision-induced dissociation measurement.

Electrogenerated IrO(x) nanoparticles as dissolved redox catalysts for water oxidation.

We describe the first example of redox catalysis using a dissolved electroactive nanoparticle, based on the oxidation of water by electrogenerated IrO(x) nanoparticles containing Ir(VI) states, in pH 13 solutions of 1.6 +/- 0.6 nm (dia.) Ir(IV)O(x) nanoparticles capped solely by hydroxide. At potentials (ca. +0.45 V) higher than the mass transport-controlled plateau of the nanoparticle Ir(V/IV) wave, rising large redox catalytic currents reflect electrochemical generation of Ir(VI) states, which by +0.55 V and onward to +1.0 V are shown by rotated ring disk electrode experiments to lead with 100% current efficiency to the oxidation of water to O(2). O(2) production at +0.55 V corresponds to an overpotential eta of only 0.29 V, relative to thermodynamic expectations of the four electron H(2)O-->O(2) reaction. The Ir site turnover frequency (TO, mol O(2)/Ir sites/s) is 8-11 s(-1). Controlled potential coulometry shows that all Ir sites in these nanoparticles (average 66 Ir each) are electroactive, meaning that the nanoparticles are small enough to allow the required electron and proton transport throughout. Both the overpotential and TO values are nearly the same as those observed previously for films electroflocculated from similar IrO(x) nanoparticles, providing the first comparison of electrocatalysis by nanoparticle films with redox catalysis by dissolved, diffusing nanoparticles.

Tandem mass spectrometry of thiolate-protected Au nanoparticles Na(x)Au25(SC2H4Ph)(18-y)(S(C2H4O)5CH3)(y).

We report the first collision-induced dissociation tandem mass spectrometry (CID MS/MS) of a thiolate-protected Au nanoparticle that has a crystallographically determined structure. CID spectra assert that dissociation pathways for the mixed monolayer Na(x)Au(25)(SC(2)H(4)Ph)(18-y)(S(C(2)H(4)O)(5)CH(3))(y) centrally involve the semi-ring Au(2)L(3) coordination (L = some combination of the two thiolate ligands) that constitutes the nanoparticle's protecting structure. The data additionally confirm charge state assignments in the mass spectra. Prominent among the fragments is [Na(2)AuL(2)](1+), one precursor of which is identified as another nanoparticle fragment in the higher m/z region. Another detected fragment, [Na(2)Au(2)L(3)](1+), represents a mass loss equivalent to an entire semi-ring, whereas others suggest involvement (fragmentation/rearrangement) of multiple semi-rings, e.g., [NaAu(3)L(3)](1+) and [NaAu(4)L(4)](1+). The detailed dissociation/rearrangement mechanisms of these species are not established, but they are observed in other mass spectrometry experiments, including those under non-CID conditions, namely, electrospray ionization mass spectrometry (ESI-MS) with both time-of-flight (TOF) and FT-ICR analyzers. The latter, previously unreported results show that even soft ionization sources can result in Au nanoparticle fragmentation, including that yielding Au(4)L(4) in ESI-TOF of a much larger thiolate-protected Au(144) nanoparticle under non-CID conditions.

Gold nanoparticles: past, present, and future.

This perspective reviews recent developments in the synthesis, electrochemistry, and optical properties of gold nanoparticles, with emphasis on papers initiating the developments and with an eye to their consequences. Key aspects of Au nanoparticle synthesis have included the two-phase synthesis of thiolated nanoparticles, the sequestration and reduction of Au salts within dendrimers, the controlled growth of larger particles of well-defined shapes via the seeded approach, and the assembling of a variety of nanoparticle networks and nanostructures. The electrochemistry of thiolated Au nanoparticles is systemized as regions of bulk-continuum voltammetry, voltammetry reflective of quantized double-layer charging, and molecule-like voltammetry reflective of molecular energy gaps. These features are principally determined by the nanoparticle core. Interesting multielectron Au nanoparticle voltammetry is observed when the thiolate ligand shell has been decorated with redox groupings. Another development is that Au nanoparticles were discovered to exhibit unanticipated properties as heterogeneous catalysts, starting with the low-temperature oxidation of CO. Substantial progress has also been made in understanding the surface plasmon spectroscopy of Au nanoparticles and nanorods. The need to investigate the optical properties of metal particles of a single, well-defined shape and size has motivated the development of a number of new techniques, leading to the study of electron transfer and redox catalysis on single nanoparticles.

Voltammetry and redox charge storage capacity of ferrocene-functionalized silica nanoparticles.

We describe the electrochemistry of 15 nm diameter silica nanoparticles densely functionalized with ferrocene (FcSiO(2)) through siloxane couplings. Each nanoparticle bears approximately 600 Fc sites, as measured by potentiometric titration (590 Fc) and diffusion-controlled voltammetry (585 Fc) and estimated by XPS (630 Fc). The nanoparticle ferrocene coverage amounts to ca. a complete monolayer of ferrocene sites, which react electrochemically without mutual interactions and which are apparently fully accessible for diffusion-controlled electrode reactions. Diffusion-controlled voltammetry of the FcSiO(2) nanoparticles was observed in dilute methanol dispersions and in more concentrated slurry phases formed in methanol/acetonitrile mixtures. Electrochemical studies reveal interesting behavior in the dilute and more concentrated solutions. Because of the large nanoparticle surface area/volume ratio, the ferrocene-coated silica nanoparticles are capable of storing up to 5 x 10(7) C/m(3) of redox charge as dry phases and 6 x 10(5) C/m(3) in the concentrated slurries.