Search results for "Charge transfer"

Charge-transfer interactions between fullerenes and a mesoporous tetrathiafulvalene-based metal–organic framework

2019

The design of metal–organic frameworks (MOFs) incorporating electroactive guest molecules in the pores has become a subject of great interest in order to obtain additional electrical functionalities within the framework while maintaining porosity. Understanding the charge-transfer (CT) process between the framework and the guest molecules is a crucial step towards the design of new electroactive MOFs. Herein, we present the encapsulation of fullerenes (C60) in a mesoporous tetrathiafulvalene (TTF)-based MOF. The CT process between the electron-acceptor C60 guest and the electron-donor TTF ligand is studied in detail by means of different spectroscopic techniques and density functional theor…

Charge Transfer Plasmons in Dimeric Electron Clusters

2020

The tunability of the optical response of dimers of metal clusters and nanoparticles makes them ideal for many applications from sensing and imaging to inducing chemical reactions. We have studied charge transfer plasmons in separate and linked dimers of closed-shell electron clusters of 8 and 138 electrons using time-dependent density functional theory. The simple model clusters enable the systematic study of the charge transfer phenomenon from the electronic perspective. To identify the charge transfer plasmons, we have developed an index, the Charge Transfer Ratio, for quantifying the charge transfer nature of the excitations. In addition, we analyze the induced transition density and th…

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…

Novel Methodologies to Model Charge Transport in Metal-Air Batteries

2018

CCD characterization and measurements automation

2012

Abstract Modern mosaic cameras have grown both in size and in number of sensors. The required volume of sensor testing and characterization has grown accordingly. For camera projects as large as the LSST, test automation becomes a necessity. A CCD testing and characterization laboratory was built and is in operation for the LSST project. Characterization of LSST study contract sensors has been performed. The characterization process and its automation are discussed, and results are presented. Our system automatically acquires images, populates a database with metadata information, and runs express analysis. This approach is illustrated on 55 Fe data analysis. 55 Fe data are used to measure …

Face-to-face held Pacman type porphyrin-fullerene dyads: design, synthesis, charge transfer interactions and photophysical studies

2008

Pacman-type face-to-face zinc-porphyrin-fullerene dyads have been newly synthesized and studied. Owing to the close proximity of the donor and acceptor entities, strong pi-pi intramolecular interactions between the porphyrin and fullerene entities resulted in modulating the spectral and electrochemical properties of the dyads. New absorption and emission bands that correspond to the charge-transfer interactions were observed in the near-IR region. Time-resolved transient absorption studies revealed efficient photoinduced electron transfer from the singlet excited porphyrin to the fullerene entity. The rate constants for photoinduced electron transfer are analyzed in terms of the Marcus theo…

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 …

Dynamic Effects on Reaction Rates in a Michael Addition Catalyzed by Chalcone Isomerase. Beyond the Frozen Environment Approach

2008

We present a detailed microscopic study of the dynamics of the Michael addition reaction leading from 6'-deoxychalcone to the corresponding flavanone. The reaction dynamics are analyzed for both the uncatalyzed reaction in aqueous solution and the reaction catalyzed by Chalcone Isomerase. By means of rare event simulations of trajectories started at the transition state, we have computed the transmission coefficients, obtaining 0.76 +/- 0.04 and 0.87 +/- 0.03, in water and in the enzyme, respectively. According to these simulations, the Michael addition can be seen as a formation of a new intramolecular carbon-oxygen bond accompanied by a charge transfer essentially taking place from the nu…

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 …