Search results for " charge transfer"

Conformational substates of ferricytochrome c revealed by combined optical absorption and electronic circular dichroism spectroscopy at cryogenic tem…

2010

We have investigated the heterogeneity of the Fe(III)–Met80 linkage of horse heart ferricytochrome c by probing the 695 nm charge transfer band with absorption and electronic circular dichroism (ECD) spectroscopy. In order to verify the connection between conformational substates of the Fe(III)–Met80 linkage and the 695 nm band spectral heterogeneity, we have performed experiments as a function of pH (neutral and acidic) and temperature (room and 20 K). At room temperature, the ECD spectrum is blue shifted with respect to the absorption one; the shift is more pronounced at acidic pH and is compatible with the presence of sub-bands. ECD measurements at 20 K highlighted the heterogeneous natu…

Tuning of the photoinduced charge transfer process in donor-acceptor "double cable" copolymers

2003

The covalent linking of acceptor molecules to electron donating conjugated polymer is an approach for the development of new photoactive materials for the fabrication of organic photoelectric conversion devices. With this strategy we have designed a polyalkylthiophene copolymer series containing in the side chain anthraquinone molecules as electron acceptor. The peculiar features of the copolymers are the good processability and the ease in tailoring the content of acceptor moieties. Their potential use as photoactive materials is investigated in terms of the photoinduced charge transfer properties, studied by FTIR photoinduced absorption and Light Induced Electron Spin Resonance spectrosco…

Synthesis by solution combustion of inorganic blue pigments MFe2(P2O7)2: Influence of the cation M (Zn2+, Co2+, Cu2+, and Mg2+) on their optical prop…

2020

Abstract The aim of this work is to find the effect of the cation M (Zn2+, Co2+, Cu2+, and Mg2+) on the optical properties of MFe2(P2O7)2 synthesized by solution combustion. The crystal structure of the powders was determined by X-ray diffraction (XRD), Infrared spectroscopy (IR), and Raman spectroscopy. The presence of Fe2+ and Fe3+ ions in the pigments was studied using Mossbauer spectroscopy (MS), these spectra showed at 298 K three well-defined Mossbauer doublets belonging to octahedral S1 site and S3 site of Fe3+ and trigonal prismatic S2 site of Fe2+, confirming the formation of ZnFe2(P2O7)2, CoFe2(P2O7)2 and MgFe2(P2O7)2 structures, while in CuFe2(P2O7)2 there is no presence of trigo…

Oligonuclear Ferrocene Amides: Mixed‐Valent Peptides and Potential Redox‐Switchable Foldamers

2010

Trinuclear ferrocene tris-amides were synthesized from an Fmoc- or Boc-protected ferrocene amino acid, and hydrogen-bonded zigzag conformations were determined by NMR spectroscopy, molecular modelling, and X-ray diffraction. In these ordered secondary structures orientation of the individual amide dipole moments approximately in the same direction results in a macrodipole moment similar to that of α-helices composed of α-amino acids. Unlike ordinary α-amino acids, the building blocks in these ferrocene amides with defined secondary structure can be sequentially oxidized to mono-, di-, and trications. Singly and doubly charged mixed-valent cations were probed experimentally by Vis/NIR, param…

Modification of Nanocrystalline WO3 with a Dicationic Perylene Bisimide: Applications to Molecular Level Solar Water Splitting

2015

[(N,N?-Bis(2-(trimethylammonium)ethylene) perylene 3,4,9,10-tetracarboxylic acid bisimide)(PF6)2] (1) was observed to spontaneously adsorb on nanocrystalline WO3 surfaces via aggregation/hydrophobic forces. Under visible irradiation (? > 435 nm), the excited state of 1 underwent oxidative quenching by electron injection (kinj > 108 s-1) to WO3, leaving a strongly positive hole (Eox ? 1.7 V vs SCE), which allows to drive demanding photo-oxidation reactions in photoelectrochemical cells (PECs). The casting of IrO2 nanoparticles (NPs), acting as water oxidation catalysts (WOCs) on the sensitized electrodes, led to a 4-fold enhancement in photoanodic current, consistent with hole transfer from …

How Hydrogen Bonds Affect Reactivity and Intervalence Charge Transfer in Ferrocenium‐Phenolate Radicals

2016

The ferrocenyl-phenol 2,4-di-tert-butyl-6-(ferrocenylcarbamoyl)phenol (H-1) forms intramolecular hydrogen bonds which are absent in its constitutional isomer 2,6-di-tert-butyl-4-(ferrocenylcarbamoyl)phenol (H-2). Their corresponding bases 1– and 2– show intra- and intermolecular NH···O hydrogen bonds, respectively. The phenolate 1– is reversibly oxidized to 1·, whereas 2– only undergoes a quasi-reversible oxidation to 2·, which suggests a higher reactivity. The radical pools of 1· and 2· formed by the oxidation/deprotonation of H-1 and H-2 have been probed by (rapid-freeze) electron paramagnetic resonance (EPR) spectroscopy and by spin-trapping techniques to elucidate the types of radicals …

Tetrathiafulvalene-Polychlorotriphenylmethyl Dyads: Influence of Bridge and Open-Shell Characteristics on Linear and Nonlinear Optical Properties

2017

Three conjugated donor-π-acceptor radical systems (1 a–1 c) were prepared by bridging a tetrathiafulvalene (TTF) electron-donor unit to a polychlorotriphenylmethyl (PTM) electron-acceptor radical through vinylene units of different lengths. The dependence of the intramolecular charge transfer on the length of the conjugated bridge has been analyzed by different electrochemical and spectroscopic techniques. Linear optical properties and the second-order nonlinear optical (NLO) response of these derivatives have been computed by comparing systems 1 a–1 c with the non-radical analogues (2 a–2 c). Interestingly, an enhanced NLO response is predicted for dyads 1 a–1 c with PTM in the radical for…

Enhanced power-conversion efficiency in organic solar cells incorporating polymeric compatibilizers

2018

Visible Light Induced Oxidation of Ferulic Acid by TiO2 Photocatalysis

2012

Oxidation of ferulic acid (C10H10O4) in aqueous medium occurs by using both commercial and home prepared TiO2 samples under visible light irradiation. Among the oxidation products vanillin was found with a selectivity ranging from 1 to 2% with respect to the converted substrate. By considering that TiO2 is unable to absorb visible light and ferulic acid does not react in the absence of TiO2, the observed photoactivity may be explained by the formation of a charge-transfer complex between ferulic acid and TiO2, being the complex able to absorb visible light. Among all the tested semiconductor oxides, only Merck anatase TiO2 does not perform the oxidation of ferulic acid under visible light i…

The origin of slow electron recombination processes in dye-sensitized solar cells with alumina barrier coatings

2004

We investigate the effect of a thin alumina coating of nanocrystalline TiO2 films on recombination dynamics of dye-sensitized solar cells. Both coated and uncoated cells were measured by a combination of techniques: transient absorption spectroscopy, electrochemical impedance spectroscopy, and open-circuit voltage decay. It is found that the alumina barrier reduces the recombination of photoinjected electrons to both dye cations and the oxidized redox couple. It is proposed that this observed retardation can be attributed primarily to two effects: almost complete passivation of surface trap states in TiO2 that are able to inject electrons to acceptor species, and slowing down by a factor of…