Search results for "Photoinduced electron transfer"
showing 10 items of 47 documents
Ship-in-a-bottle synthesis of triphenylamine inside faujasite supercages and generation of the triphenylamminium radical ion
2005
Abstract The ship-in-a-bottle synthesis of triphenylamine encapsulated within basic X zeolite has been accomplished by reacting sodium diphenylamide with bromobenzene in the presence of a bifunctional palladium (Hartwig–Buchwald conditions). The presence of incarcerated triphenylamine was demonstrated by dissolving the zeolite with concentrated HF and analyzing the organic material in the dichloromethane extract. Laser flash photolysis (266 nm) gives rise to the generation of triphenylamminium radical cation detected as a transient species decaying in hundreds of microseconds. Upon repetitive cyclic voltammograms, zeolite encapsulated triphenylamine shows a reversible oxidation–reduction pr…
Enhanced electronic communication through a conjugated bridge in a porphyrin-fullerene donor-acceptor couple
2021
A ZnP-2EDOTV-C60 triad, with enhanced electronic communication between terminus donor and acceptor moieties, was synthesized and studied both experimentally and theoretically. Electrochemical measurements and density functional theory calculations support that the first oxidation takes place on the 3,4-ethylenedioxythiophenevinylene (2EDOTV) bridge followed by the oxidation of the ZnP moiety at slightly higher energies. The electronic communication between the terminal electron-donor ZnP and the electron-acceptor C60 units is enhanced by the conjugated EDOTV-based spacer leading to photoinduced electron transfer over the distance >2 nm in the picosecond time domain. The involvement of the s…
Fluorescence Quenching in BODIPYs Having Ir‐ and Rh‐Tethered Complexes
2016
The effect of Rh- and Ir-centers on the optical properties of the BODIPY core has been studied. To this end, novel metal complexes tethered to BODIPY have been prepared through an easy and versatile procedure using N-directed C–H activation reactions. The organometallic moiety has a tremendous influence on the emissive properties of the BODIPY fragment. A photoinduced electron transfer (PET) mechanism is suggested to be the main mechanism responsible for the suppression of the BODIPY fluorescence emission in the newly formed dyads. The efficiency of the PET depends on both the distance between the chromophores in the dyad and the nature of the transition metal (Rh vs. Ir).
Photoinduced Electron Transfer in Multiporphyrinic Interlocked Structures: The Effect of Copper(I) Coordination in the Central Site
2004
Photoinduced processes have been determined in a [2]catenane containing a zinc(II) porphyrin, a gold(III) porphyrin, and two free phenanthroline binding sites, Zn-Au(+), and in the corresponding copper(I) phenanthroline complex, Zn-Cu(+)-Au(+). In acetonitrile solution Zn-Au(+) is present in two different conformations: an extended one, L, which accounts for 40 % of the total, and a compact one, S. In the L conformation, the electron transfer from the excited state of the Zn porphyrin to the gold-porphyrin unit (k = 1.3x10(9) s(-1)) is followed by a slow recombination (k = 8.3x10(7) s(-1)) to the ground state. The processes in the S conformation cannot be clearly resolved but a charge-separ…
Gold(II) Porphyrins in Photoinduced Electron Transfer Reactions
2019
Chemistry - a European journal 25(23), 5940 - 5949 (2019). doi:10.1002/chem.201900050
Synthesis, Electrochemistry, and Photophysics of Aza-BODIPY Porphyrin Dyes
2016
International audience; The synthesis of dyad and triad aza-BODIPY-porphyrin systems in two steps starting from an aryl-substituted aza-BODIPY chromophore is described. The properties of the resulting aza-BODIPY-porphyrin conjugates have been extensively investigated by means of electrochemistry, spectroelectrochemistry, and absorption/emission spectroscopy. Fluorescence measurements have revealed a dramatic loss of luminescence intensity, mainly due to competitive energy transfer and photoinduced electron transfer involving charge separation followed by recombination.
Charge Transfer Transitions in Neutral and Ionic Polypeptides: A Theoretical Study
2001
We report on the vertical electronic excitation spectra of neutral polypeptides and their radical ions. Model systems including tri-, tetra-, and octamers in an α-helix and β-sheet alike conformation are studied by various computational methods. The results allow us to assign the band centered at about 7.5 eV in the absoption spectra of proteins to charge transfer states. The calculations also support conclusions from recent experiments which propose charge transfer as a possible mechanism for photoinduced electron transfer in polypeptide cations.
Bis- and trisporphyrin bio-inspired models for bacterial antennas and photosystems
2011
This review presents the synthetic aspects and photophysical properties of trimeric systems constructed with a first unit consisting of a cofacial porphyrin and then of another porphyrin attached as a side arm. Two scenarios are dealt with. The first one is the case where the three chromophores are different, called donor 1–donor 2–acceptor, specifically where the cofacial fragment is composed of donor 1 and donor 2, and the side arm is the acceptor. They are considered as models for the apo-proteins used in the LH II (light harvesting device) in the purple photosynthetic bacteria. The second one is the case where the chromophores of the cofacial bisporphyrin residue are identical and are …
A photoresponsive graphene oxide-C60 conjugate.
2014
An all-carbon donor-acceptor hybrid combining graphene oxide (GO) and C60 has been prepared. Laser flash photolysis measurements revealed the occurrence of photoinduced electron transfer from the GO electron donor to the C60 electron acceptor in the conjugate
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…