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PubMed2005

CVD growth of N-doped carbon nanotubes on silicon substrates and its mechanism.

In the present study, we report the chemical vapor deposition (CVD) of nitrogen-doped (N-doped) aligned carbon nanotubes on a silicon (Si) substrate using ferrocene (Fe(C5H5)2) as catalyst and acetonitrile (CH3CN) as the carbon source. The effect of experimental conditions such as temperature, gaseous environment, and substrates on the structure and morphology of N-doped carbon nanotubes arrays is reported. From XPS and EELS data, it was found that the nitrogen content of the nanotubes could be determined over a wide range, from 1.9% to 12%, by adding the addition of hydrogen (H2) to the reaction system. It was also shown by SEM that N-doped carbon nanotube arrays could be produced on Si and SiO2 substrates at suitable temperatures, although at different growth rates. Using these concentrations, it was possible to produce three-dimensional (3D) carbon nanotubes architectures on predetermined Si/SiO2 patterns. The mechanism underlying the effect of nitrogen containing carbon sources on nanotube formation was explored using X-ray photoelectron spectroscopy (XPS).

Acetonitriles↗
PubMed2005

Molecular rectification of a helical peptide with a redox group in the metal-molecule-metal junction.

A helical hexadecapeptide immobilized on gold via a thiophenyl group at the N-terminal was analyzed by scanning tunneling microscopy under ultrahigh vacuum to obtain the I-V response at a molecular level. The attenuation factor of the electron transfer through the hexadecapeptide was determined by applying the Simons model to the I-V response to show better molecular conductance of the hexadecapeptide than dodecanethiol. Chemical modification at the C-terminal of the hexadecapeptide with a ferrocene unit, on the other hand, brought about significant changes in the I-V response, where the helical peptide became more conductive at the negative bias voltage. The molecular rectification behavior is due to the ferrocene unit regulating the direction of the electron transfer at the metal-molecule junction.

Aminoisobutyric Acids↗
PubMed2006

Single-component and mixed ferrocene-terminated alkyl monolayers covalently bound to Si(111) surfaces.

Self-assembled ferrocene monolayers covalently bound to monocrystalline Si(111) surfaces have been prepared from the attachment of an amine-substituted ferrocene derivative to a pre-assembled acid-terminated alkyl monolayer using carbodiimide coupling. This derivatization strategy yielded nanometer-scale clean, densely packed monolayers, with the ferrocene units being more than 20 A from the semiconductor surface. The amount of immobilized electroactive units could be varied in the range 2 x 10(-11) to approximately 3.5 x 10(-10) mol cm(-2) by diluting the ferrocene-terminated chains by inert n-decyl chains. The highest coverage obtained for the single-component monolayer corresponded to 0.25-0.27 bound ferrocene per surface silicon atom. The electrochemical characteristics of the mixed n-decyl/ferrocene-terminated monolayers were found to not depend significantly on the surface coverage of ferrocene units. The reversible one-electron wave of the ferrocene/ferrocenium couple was observed at E degrees ' = 0.50 +/- 0.01 V vs SCE, and the rate constant of electron transfer kapp was about 50 s(-1).

Alkylation↗
PubMed2006

Combined X-ray absorption spectroscopy and density functional theory examination of ferrocene-labeled peptides.

A combination of soft X-ray absorption spectroscopy (XAS) measurements and StoBe density functional theory (DFT) calculations has been used to study the electronic structures of the ferrocene-labeled peptides Fc-Pro(n)-OBz (n = 1-4). Excellent agreement between the measured and the simulated data is observed in all cases, and the origin of all major spectral features was assigned. The breaking of the degeneracy of the ferrocene 3e(2u)-like unoccupied molecular orbital under the influence of a substituent attached to a Cp ring was observed experimentally. The influence of the bonding environment on the O 1s and N 1s XAS spectra was examined. A corrected assignment of one of the major features in the Fe 2p XAS spectra of ferrocene is proposed and supported by the DFT simulations, as well as the measured spectra.

Ferrous Compounds↗
PubMed2006

Rate of interfacial electron transfer through the 1,2,3-triazole linkage.

The rate of electron transfer is measured to two ferrocene and one iron tetraphenylporphyrin redox species coupled through terminal acetylenes to azide-terminated thiol monolayers by the Cu(I)-catalyzed azide-alkyne cycloaddition (a Sharpless "click" reaction) to form the 1,2,3-triazole linkage. The high yield, chemoselectivity, convenience, and broad applicability of this triazole formation reaction make such a modular assembly strategy very attractive. Electron-transfer rate constants from greater than 60,000 to 1 s(-1) are obtained by varying the length and conjugation of the electron-transfer bridge and by varying the surrounding diluent thiols in the monolayer. Triazole and the triazole carbonyl linkages provide similar electronic coupling for electron transfer as esters. The ability to vary the rate of electron transfer to many different redox species over many orders of magnitude by using modular coupling chemistry provides a convenient way to study and control the delivery of electrons to multielectron redox catalysts and similar interfacial systems that require controlled delivery of electrons.

Alkynes↗
PubMed2006

Direct calculation of electron transfer parameters through constrained density functional theory.

It is shown that constrained density functional theory (DFT) can be used to access diabatic potential energy surfaces in the Marcus theory of electron transfer, thus providing a means to directly calculate the driving force and the inner-sphere reorganization energy. We present in this report an analytic expression for the forces in constrained DFT and their implementation in geometry optimization, a prerequisite for the calculation of electron transfer parameters. The method is then applied to study the symmetric mixed-valence complex tetrathiafulvalene-diquinone radical anion, which is observed experimentally to be a Robin-Day class II compound but found by DFT to be in class III. Constrained DFT avoids this pitfall of over-delocalization and provides a way to find the charge-localized structure. In another application, driving forces and inner-sphere reorganization energies are calculated for the charge recombination (CR) reactions in formanilide-anthraquinone (FA-AQ) and ferrocene-formanilide-anthraquinone (Fc-FA-AQ). While the two compounds have similar reorganization energies, the driving force in FA-AQ is 1 eV larger than in Fc-FA-AQ, in agreement with experimental observations and supporting the experimental conclusion that the anomalously long-lived FA-AQ charge-separated state arises because the electron transfer is in the Marcus inverted region.

Anions↗
PubMed2006

Small molecule chemisorption on indium-tin oxide surfaces: enhancing probe molecule electron-transfer rates and the performance of organic light-emitting diodes.

Indium-tin oxide (ITO) surfaces have been modified by chemisorption of carboxylic acid functionalized small molecules: ferrocene dicarboxylic acid (1), 3-thiophene acetic acid (2), and 6-{4-[{4'-[[4-(5-carboxy-pentyloxy)-phenyl]-(4-methoxy-phenyl)-amino]-biphenyl-4-yl}-(4-methoxy-phenyl)-amino]-phenoxy}-hexanoic acid (p-OMe)2-TPD-(C5-COOH)2) (3). Voltammetrically determined surface coverages of 1-3 increased in two stages, the first stage completing in minutes, the latter stage taking several hours. Electron-transfer rate coefficients, kS, for the probe molecule ferrocene in acetonitrile likewise increased in two stages with increasing surface coverages of 1, 2, and 3. Fourier transform infrared spectroscopy of In2O3 powders, exposed for long periods to ethanol solutions of each modifier, confirmed the formation of indium oxalate-like surface species. X-ray photoelectron spectroscopy of carboxy-terminated alkanethiol-modified gold surfaces, exposed to these same In2O3(powder)/small molecule modifier solutions, showed the capture of trace levels of indium as a result of the chemisorption of these small molecules, suggesting that slow etching of the ITO surface also occurs during the chemisorption event. Conventional aluminum quinolate/bis-triarylamine organic light-emitting diodes (OLEDs) created on ITO surfaces modified with 1, 2, and 3, with and without an overlayer of PEDOT:PSS (a poly(thiophene)/poly(stryenesulfonate) ITO modifier), showed leakage currents lowered by several orders of magnitude and an increase in OLED device efficiency.

Acetates↗
PubMed2006

Design and studies on supramolecular ferrocene-porphyrin-fullerene constructs for generating long-lived charge separated states.

Supramolecular ferrocene-porphyrin-fullerene constructs, in which covalently linked ferrocene-porphyrin-crown ether compounds were self-assembled with alkylammonium cation functionalized fullerenes, have been designed to achieve stepwise electron transfer and hole shift to generate long-lived charge separated states. The adopted crown ether-alkylammonium cation binding strategy resulted in stable conjugates as revealed by computational studies performed by the DFT B3LYP/3-21G(*) method in addition to the binding constants obtained from fluorescence quenching studies. The free-energy changes for charge-separation and charge-recombination were varied by the choice of different metal ions in the porphyrin cavity. Free-energy calculations suggested that the light-induced electron-transfer processes from the singlet excited state of porphyrins to be exothermic in all of the investigated supramolecular dyads and triads. Photoinduced charge-separation and charge-recombination processes have been confirmed by the combination of the time-resolved fluorescence and nanosecond transient absorption spectral measurements. In case of the triads, the charge-recombination processes of the radical anion of the fullerene moiety take place in two steps, viz., a direct charge recombination from the porphyrin cation radical and a slower step involving distant charge recombination from the ferrocene cation moiety. The rates of charge recombination for the second route were found to be an order of magnitude slower than the former route, thus fulfilling the condition for charge migration to generate long-lived charge-separated states in supramolecular systems.

Cations↗
PubMed2006

Measurement and DFT calculation of Fe(cp)(2) redox potential in molecular monolayers covalently bound to H-Si(100).

The electron transfer to self-assembled molecular monolayers carrying a ferrocene (Fc) center, grafted on a flat Si(100) surface, is a recent subject of experimental investigation. We report here the density functional theory (DFT) ab initio calculation of Fc-silicon hybrid redox potentials. The systems were modeled with a slab of H-terminated Si(100) 1 x 1 and 2 x 1 surfaces: geometries were optimized using the ONIOM method, and solute-solvent interactions were included through the polarizable continuum model (PCM) method. Two new routes for Si functionalization with ethyl- (EtFC) and ethynyl-Fc (EFC) differing only in the unsaturation degree of the anchoring arm have been successfully explored, and the redox potential of the resulting hybrids has been measured by cyclic voltammetry: 0.675 and 0.851 V versus NHE for the EtFC and EFC derivatives, respectively. These values, along with the previously measured potential (0.700 V) for the mono-unsaturated derivative, vinyl-Fc, allow the relation between the unsaturation degree and the adduct redox potential to be studied. The comparison among the measured and computed potentials allows one to discriminate between different adduct isomers for the saturated species and more importantly provides strong indications that the carbon-carbon unsaturation initially present in the molecular arm used for anchoring to the surface is preserved upon addition, in contrast with the commonly accepted reaction mechanism.

Algorithms↗
PubMed2004

Immobilization of the nanoparticle monolayer onto self-assembled monolayers by combined sterically enhanced hydrophobic and electrophoretic forces.

The immobilization of surface-derivatized gold nanoparticles onto methyl-terminated self-assembled monolayers (SAMs) on gold surface was achieved by the cooperation of hydrophobic and electrophoretic forces. Electrochemical and scanning probe microscopy techniques were utilized to explore the influence of the SAM's structure and properties of the nanoparticle/SAM/gold system. SAMs prepared from 1-decanethiol (DT) and 2-mercapto-3-n-octylthiophene (MOT) were used as hydrophobic substrates. The DT SAM is a closely packed and organized monolayer, which can effectively block the underlying gold and inhibit a variety of solution species including organic and inorganic molecules from penetrating, whereas the MOT monolayer is poorly packed or disorganized (because of a large difference in dimension between the thiophene head and the alkylchain tail) and permeable to many organic probes in aqueous solution but not to inorganic probes. Thus, the MOT monolayer provides a more energetically favorable hydrophobic surface for the penetration and adsorption of organic species than the DT monolayer. This hypothesis is supported by experiments in which the density of hydrophobically immobilized nanoparticles on the MOT SAM is much larger than that on the DT SAM. The results also suggest new approaches for modification of macroscopic surfaces with nanoscopic particles.

Electrochemistry↗
PubMed2004

Electrochemical redox control of ferrocene using a supramolecular assembly of ferrocene-linked C(60) derivative and metallooctaethylporphyrin array on a Au(111) electrode.

Supramolecular assembled layers of ferrocene-linked C(60) derivative (C(60)Fc) and various metal ions coordinated to octaethylporphyrin (MOEP) were formed on the surface of a Au(111) single-crystal electrode by immersing the Au substrate successively into a benzene solution containing MOEP and one containing C(60)Fc molecules. The MOEPs used were zinc(II) (ZnOEP), cobalt(II) (CoOEP), copper(II) (CuOEP), and iron(III) chloride (FeClOEP) of OEP (2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine). The molecules of C(60)Fc directly attached to the Au(111) electrode showed poorly defined electrochemical redox response, whereas a clear electrochemical redox reaction of the ferrocene group in the C(60)Fc molecule was observed at 0.78 V versus reversible hydrogen electrode on ZnOEP, CoOEP, and CuOEP adlayers, but not on the FeClOEP adlayer. Adlattices of the underlying layer and the top layer of C(60)Fc were determined by in situ scanning tunneling microscopy. Adlayer structures of MOEP were independent of the central metal ion; that is, MOEP molecules were arranged hexagonally with two different orientations. Highly ordered C(60)Fc arrays were formed with 1:1 composition on the ZnOEP-, CoOEP-, and CuOEP-modified Au(111) surface, whereas a disordered structure of C(60)Fc was found on the FeClOEP-modified Au(111) surface. The presence of Cl ligand was found to prevent the formation of supramolecularly assembled layers with C(60)Fc molecules, resulting in an ill-defined unclear electrochemical response of the Fc group. The well-defined electrochemical response of the Fc group in C(60)Fc was clearly due to the control of orientation of C(60)Fc molecules.

Electrochemistry↗
PubMed2004

Synthesis and redox behavior of biferrocenyl-functionalized ruthenium(II) terpyridine gold clusters.

Spectroscopic and electrochemical characterizations of ferrocene- and biferrocene-functionalized terpyridine octanethiolate monolayer-protected clusters were investigated and reported. The electrochemical measurements of Ru2+ coordinated with 4'-ferrocenyl-2,2':6',2' '-terpyridine and 4'-biferrocenyl-2,2':6',2' '-terpyridine complexes were dominated by the Ru2+/Ru3+ redox couple (E(1/2) at approximately 1.3 V), Fe(2+)/Fe(3+) redox couples (E(1/2) from approximately 0.6 to approximately 0.9 V), and terpy/terpy-/terpy2- redox couples (E(1/)(2) at ca. -1.2 and ca. -1.4 V). The substantial appreciable variations detected in the Ru2+/Ru3+ and Fe2+/Fe3+ oxidation potentials indicate that there is an interaction between the Ru2+ and Fe2+ metal centers. The coordination of the Ru2+ metal center with 4'-ferrocenyl-2,2':6',2' '-terpyridine and 4'-biferrocenyl-2,2':6',2' '-terpyridine leads to an intense 1[(d(pi)Fe)6] --> 1[d(pi)Fe)5(pi*terpyRu)1] transition in the visible region. The 1[(d(pi)Fe)6] -->1[d(pi)Fe)5(pi*terpyRu)1] transition observed at approximately 510 nm revealed that there was a qualitative electronic coupling between metal centers. The coordination of the Ru2+ transition metal center lowers the energy of the pi*terpy orbitals, causing this transition.

Electrochemistry↗
PubMed2004

Attachment of ferrocene nanotubes on beta-cyclodextrin self-assembled monolayers with molecular recognitions.

Ferrocene nanotubes were fabricated by binding carboxylic acid-derivatized ferrocenes onto template peptide nanotubes via hydrogen bonding. When these ferrocene-functionalized nanotubes were incubated with beta-cyclodextrin (beta-CD) self-assembled monolayers (SAMs) coated on patterned Au substrates in solution, the ferrocene nanotubes recognized and attached onto the beta-CD SAMs via host-guest molecular recognition. The ferrocene nanotubes were also observed to recognize the certain cavity size of CD. The attachment/detachment of nanotubes on the beta-CD SAMs was controlled electrochemically by tuning the redox states of ferrocene nanotubes. This electric field-responsive building block may be applied to build nanometer-sized switching components in electronics and sensors.

Carbohydrate Sequence↗
PubMed2005

Synthesis of ferrocene-grafted poly(p-phenylene-ethynylenes) and control of electrochemical behaviors of their thin films.

New ferrocene-coated poly(p-phenylene-ethynylenes) (PPEs) with end capping groups of protected thiol were prepared by a palladium-catalyzed Sonogashira coupling reaction. Ferrocene groups were covalently attached to polymers A and B through ethylene oxide tethers and to polymer C through methylene tethers. Polymers A and B are soluble in common solvents such as tetrahydrofuran (THF), chloroform, methylene chloride, acetone, dimethylformamide (DMF), and dimethyl sulfoxide (DMSO), and polymer C is soluble in toluene, THF, chloroform, and methylene chloride. Polymers A-C display low quantum yield, caused by electron-transfer quenching of ferrocene groups as electron donors. The polymer thin films were prepared through incubation of gold electrodes in THF solutions containing the polymers for 2 days. Ferrocene in thin films of polymers A and B display significantly faster electron-transfer rate than that of polymer C. Hydrophilic ethylene oxide side chains of polymers A and B decrease formal potential of tethered ferrocene groups because of electron-donating effect from ethylene oxide side chains, which stabilizes the ferrocenium ion and leads to a cathodic shift of the redox wave.

Alkynes↗
PubMed2005

Electron transfer in metal-molecule-metal junction composed of self-assembled monolayers of helical peptides carrying redox-active ferrocene units.

Electronic properties of three kinds of helical peptides with or without redox-active ferrocene units were investigated by using scanning tunneling microscopy under ultrahigh vacuum. The currents through the helical peptides carrying ferrocene units at the molecular terminals became significantly larger than that through a reference peptide without any ferrocene units. On the other hand, ferrocene units in the middle of the peptide chain did not affect the current-voltage characteristics. These results indicate that the ferrocene units near the metal electrode should play an important role for efficient electron transfer between the metal and the peptide molecules, which process is one of the rate-determining steps for characterizing molecular conductance in metal-molecule-metal junction.

Electrons↗
PubMed2006

Redox-active biomolecular architectures and self-assembled monolayers based on a cyclodecapeptide regioselectively addressable functional template.

A nanometer scale redox active biomolecular architecture has been successfully synthesized through an efficient chemoselective oxime based coupling between ferrocenyl groups and a regioselectively addressable cyclodecapeptide. This molecular tool exhibits electronic, structural, and chemical properties driven by the biomimetic recognition activity of the polypeptide skeleton associated to the well-defined electrochemical activity of metallocenyl probes. Biomolecular materials obtained by confinement of the redox cyclopeptide in self-assembled monolayers on gold surfaces shows efficient through-bond electron transfer from the ferrocenes to the electrode surface via the peptidic backbone, as well as markedly improved sensing properties toward anionic species in organic electrolyte, as compared to those observed in homogeneous solution.

Cyclization↗
PubMed2006

Voltammetry of suspensions of hollow particles with ferrocene-immobilized polyallylamine shells.

Redox-active hollow spheres were prepared through extracting a polystyrene core from the latex particle (PSPAAFc) composed of the core and the polyallylamine shell including ferrocenyl carboxylic amide. The suspension of the hollow spheres showed anodic and cathodic voltammetric peaks, which were nearly reversible and diffusion-controlled. The current was 3 times as large as the current for the suspension of the filled PSPAAFc. This value agreed with the theoretical one evaluated from the diameter (1.28 microm), the number of ferrocenyl moieties per particle, 1.2 x 108, by UV spectroscopy, and the diffusion coefficient obtained from the Stokes-Einstein equation. This fact indicates the reaction of the whole loaded charge, in contrast to the partial charge transfer of PSPAAFc. The dynamic flattening motion was observed to support the reaction of the whole charge.

Ferrous Compounds↗
PubMed2006

Conducting metallopolymers based on azaferrocene.

A series of 2,5-thiophene-substituted 1',2',3',4',5'-pentamethylazaferrocene complexes were synthesized and electropolymerized to produce polymers with fully pi-conjugated backbones. The length and hence oxidation potential of the conjugated linker (the thiophene fragments) between the metal centers were varied to understand the influence of the metal-metal interactions on the overall electroactivity of the resulting polymer. These complexes were electrochemically polymerized, and the resulting polymers were characterized by cyclic voltammetry, in situ conductivity, and spectroelectrochemistry measurements. The iron-centered oxidations significantly increased the conductivity of the polymer. The results reveal that shorter conjugated linkers cause the onset of conductivity to occur at lower potentials. This effect implies that a superexchange mechanism is likely operative in the charge migration of these polymers.

Aza Compounds↗