Search results for "Excited state"
showing 10 items of 1387 documents
Temperature dependence of the non-local spin Seebeck effect in YIG/Pt nanostructures
2017
We study the transport of thermally excited non-equilibrium magnons through the ferrimagnetic insulator YIG using two electrically isolated Pt strips as injector and detector. The diffusing magnons induce a non-local inverse spin Hall voltage in the detector corresponding to the so-called non-local spin Seebeck effect (SSE). We measure the non-local SSE as a function of temperature and strip separation. In experiments at room temperature we observe a sign change of the non-local SSE voltage at a characteristic strip separation d0, in agreement with previous investigations. At lower temperatures however, we find a strong temperature dependence of d0. This suggests that both the angular momen…
Ring splitting of azetidin-2-ones via radical anions
2012
The radical anions of azetidin-2-ones, generated by UV-irradiation in the presence of triethylamine, undergo ring-splitting via N-C4 or C3-C4 bond breaking, leading to open-chain amides. This reactivity diverges from that found for the neutral excited states, which is characterised by alpha-cleavage. The preference for beta-cleavage is supported by DFT theoretical calculations on the energy barriers associated with the involved transition states. Thus, injection of one electron into the azetidin-2-one moiety constitutes a complementary activation strategy which may be exploited to produce new chemistry.
Purely organic Vis-to-UV upconversion with an excited annihilator singlet beyond 4 eV
2022
The conversion of visible light into high-energy UV photons via sensitized triplet–triplet annihilation (TTA-UC) could pave the way for several energy-demanding applications. However, only a handful of annihilator chromophores for Vis-to-UV upconversion are known and the current limit for the excited-state energy of the UV emitter in TTA-UC schemes is below 4 eV, i.e., in the spectral region (>310 nm) where the sun still provides a considerable photon flux. Herein, we present a novel biphenyl-based annihilator with a highly fluorescent singlet state at 4.04 eV. This annihilator can be combined with a widely-used TADF sensitizer to yield an efficient blue-light (2.77 eV) driven upconversion …
Supramolecular interactions of hexacyanocobaltate(III) with polyamine receptors containing a terminal anthracene sensor
2003
Abstract The fluorescence emission properties of a series of chemosensors containing a polyamine receptor bearing an anthracene signaling unit were studied. The fluorescence emission intensity is dependent on the protonation degree of the receptor, the fully protonated form exhibiting the highest emission intensity. By removing protons from the nitrogens a quenching effect can be observed, due to an electron-transfer from the amine to the excited fluorophore. The rate constant of the quenching process is exponentially dependent on the distance of the nitrogen from which the electron is transferred (β=0.6 A−1). The ability of the chemosensors for signaling anions was tested through the model…
Switching from intramolecular energy transfer to intramolecular electron transfer by the action of pH and Zn2+ co-ordination
2002
Abstract Intramolecular electron (eT) and energy transfer (ET) have shown to occur in a covalently linked donor–acceptor (CLDA) system consisting of a naphthalene donor covalently linked through a polyamine chain connector to an anthracene acceptor; the connector has been chosen in order to switch ON or OFF the energy flux as a function of its protonation state as well as by co-ordination to Zn 2+ . The largest energy transfer efficiency ( η =0.61) occurs for the fully protonated form (pH 9 (eT) from the lone pairs of the nitrogens to the excited fluorophore takes place, leading to complete quenching of the emission. On the other hand at neutral and basic pH values, co-ordination of Zn 2+ p…
Intramolecular electronic excitation energy transfer in donor∕acceptor dyads studied by time and frequency resolved single molecule spectroscopy
2008
Electronic excitation energy transfer has been studied by single molecule spectroscopy in donor/acceptor dyads composed of a perylenediimide donor and a terrylenediimide acceptor linked by oligo(phenylene) bridges of two different lengths. For the shorter bridge (three phenylene units) energy is transferred almost quantitatively from the donor to the acceptor, while for the longer bridge (seven phenylene units) energy transfer is less efficient as indicated by the occurrence of donor and acceptor emission. To determine energy transfer rates and efficiencies at the single molecule level, several methods have been employed. These comprise time-correlated single photon counting techniques at r…
Towards the understanding at the molecular level of the structured-water absorption and fluorescence spectra: a fingerprint of π-stacked water
2013
An intriguing absorption peak around ∼270 nm (4.59 eV) has been recurrently recorded in aqueous solutions of salts, sugars, amino acids, in the free-solute zone (exclusion zone) adjacent to various hydrophilic surfaces, as well as a transient in the conversion process of ice to water. The corresponding associated fluorescence has been observed in the interval 480–490 nm (2.58–2.53 eV). The spectroscopic features have been related to the presence of structured water but its nature remains incompletely understood. On the basis of high-level ab initio computations, the main absorption feature of structured water is assigned to the presence of two π-stacked ground-state water molecules, prefera…
Photophysics and photostability of adenine in aqueous solution: A theoretical study
2010
Abstract The sequential Monte Carlo/CASPT2 approach was employed to investigate deactivation and emission processes from the lowest-lying ππ∗ and n π∗ excited states of 9H-adenine in aqueous solution. It is found that conical intersections connecting the ππ∗ and n π∗ states with the ground state are also present in solution, whereas the barriers for the deactivation paths are significantly smaller on solvated conditions. The large destabilization of the n π∗ state found in solution possibly prevents its involvement in the deactivation photophysics and explains the change from a bi- to a mono-exponential decay for the molecule in the gas phase and solution, respectively.
Polyamine Linear Chains Bearing Two Identical Terminal Aromatic Units. Evidence for a Photo Induced Bending Movement
2001
Abstract Several chemosensors bearing a fluorescent unit at both ends of a linear polyamine chain were synthesised. The protonation as well as the association constants with Cu2+ and Zn2+ were determined by potentiometry in 0.15 mol dm−3 NaCl at 298.1 K. In the case of 1,16-bis(1-naphthylmethyl)-1,4,7,10,13,16-hexaazadecane hexahydrochloride (L1), formation of an excimer emission in aqueous acidic solutions was observed. The system was characterized by steady state fluorescence emission and by time resolved fluorescence. In the ground state the molecule is expected to adopt a more or less linear conformation, while in the excited state a bending movement of the chain must occur in order to …
Polychromatic femtosecond fluorescence studies of metal–polypyridine complexes in solution
2011
Femtosecond-resolved broadband fluorescence studies are reported for[ M(bpy)(3)](2+) (M = Fe, Ru), RuN3 and RuN719 complexes in solution. We investigated the pump wavelength dependence of the fluorescence of aqueous [ Fe(bpy)(3)](2+) and the solvent and ligand dependence of the fluorescence of Ru-complexes excited at 400 nm. For all complexes, the (MLCT)-M-1 fluorescence appears at zero time delay with a mirror-like image with respect to the absorption. It decays in <= 30-45 fs due to intersystem crossing to the (MLCT)-M-3 states, but a longer lived component of similar to 190 fs additionally shows up in RuN719 and RuN3. No solvent effects are detected. The very early dynamics are character…