Search results for "iTED"
showing 10 items of 2408 documents
Chiral synthetic pseudopeptidic derivatives as triplet excited state quenchers
2009
The behavior of 6 pseudopeptidic models, synthesized by connecting different protected amino acids (Trp, Tyr, Phe, and Lys) with various diamino spacers, as quenchers of the triplet excited state of tiaprofenic acid (and its methyl ester), has been investigated. A series of quenching constants have been determined, which depend on the nature of the quencher and on the stereochemistry of the excited drug. A significant degree of stereodifferentiation has been found for the peptidomimetic synthesized with Phe and Tyr linked by a piperazine bridge. The obtained results support the utility of laser flash photolysis (LFP) as a tool to investigate the interactions between photoexcited drugs and s…
Bistable Hofmann-Type FeII Spin-Crossover Two-Dimensional Polymers of 4-Alkyldisulfanylpyridine for Prospective Grafting of Monolayers on Metallic Su…
2021
Aiming at investigating the suitability of Hofmann-type two-dimensional (2D) coordination polymers {FeII(Lax)2[MII(CN)4]} to be processed as single monolayers and probed as spin crossover (SCO) junctions in spintronic devices, the synthesis and characterization of the MII derivatives (MII = Pd and Pt) with sulfur-rich axial ligands (Lax = 4-methyl- and 4-ethyl-disulfanylpyridine) have been conducted. The thermal dependence of the magnetic and calorimetric properties confirmed the occurrence of strong cooperative SCO behavior in the temperature interval of 100-225 K, featuring hysteresis loops 44 and 32.5 K/21 K wide for PtII-methyl and PtII/PdII-ethyl derivatives, while the PdII-methyl deri…
Toward Understanding the Photochemistry of Photoactive Yellow Protein: A CASPT2/CASSCF and Quantum Theory of Atoms in Molecules Combined Study of a M…
2009
Photochemical processes that take place in biological molecules have become an increasingly important research topic for both experimentalists and theoreticians. In this work, we report the reaction mechanism of a model of the photoactive yellow protein (PYP) chromophore in vacuo. The results obtained here, using a strategy based on the simultaneous use of the minimum energy path concept and the quantum theory of atoms in molecules applied to this excited state process, suggest a possible way in which the protein could increase the efficiency of the reaction. The role played by other electronic states of the same and different spin multiplicities in the reaction process is also analyzed, wi…
Effective conjugation in conjugated polymers with strongly twisted backbones: A case study on fluorinated MEHPPV
2016
Conjugated polymers with strongly twisted backbones, such as MEHPPV with fluorinated vinylene units (F-MEHPPV), demand a redefinition of the all-important ‘effective conjugation length’ ECL, which we extract here by a facile graphical method. In MEHPPV (being essentially planar), the ECL coincides with the ‘maximum conducive chain length’ MCC and extends over about n ≈ 9 repetition units (RU). In F-MEHPPV, the MCC is similarly long with n ≈ 8, but the ECL localizes on just one RU. The strong twist in F-MEHPPV persists in the excited state, broadening the emission spectrum and quenching the fluorescence with reduced radiative and enhanced non-radiative rates.
Localized states in wide-gap oxide glasses
1997
Localized states manifest themselves by light absorption at the optical gap of a glass and by luminescence excited there with Stoke's shift. They are created by the minority structural motifs of one or many structural modifications in which a material can exist, and which can provide electronic states absorption at the optical gap. Their wavefunctions overlapping determine the luminescence intensity dependence on the temperature [I(T)on the order of magnitude exp(- T/T 0 )] and power law (t -1 ) of luminescence decay kinetics, which include intra-center processes due to triplet-singlet transitions and recombination processes due to a tunnel and overbarrier transitions, as well as a fast com…
Ground and excited state properties of polyamine chains bearing two terminal naphthalene units
2002
A series of compounds bearing two naphthalene units linked through methylene groups to both ends of different open-chain polyamines has been investigated. The fluorescence emission studies show the presence of an excimer species whose formation depends on the protonation state and length of the polyamine chains and implies the existence of a bending movement in the excited state allowing the two naphthalene units to approach and interact. This interpretation was clearly proven by time-resolved fluorescence with the appearance of double exponential decays with a rise time observed at the excimer emission wavelength. For comparison purposes one bis-chromophoric compound containing a rigid cha…
Theoretical Studies of the Electronic Spectra of Organic Molecules
1995
The complete active space (CAS) SCF method in conjunction with multiconfigurational second-order perturbation theory (CASPT2) has been used to study the electronic spectra of a large number of molecules. The wave functions and the transition properties are computed at the CASSCF level, while dynamic correlation contributions to the excitation energies are obtained through the perturbation treatment. The methods yield energies, which are accurate to at least 0.2 eV, except in a few cases, where the CASSCF reference function does not characterize the electronic state with sufficient accuracy. The applications comprise: the polyenes from ethene to octatetraene (cis- and trans-forms); a number …
Origin of the temperature dependence of the rate of singlet energy transfer in a three-component truxene-bridged dyads
2014
We report a truxene-based dyad built upon one donor (tri-meso-phenylzinc(II)porphyrin) and two acceptors (octa-β-alkylporphyrin free base) in which the donor exhibits free rotation around a Ctruxene-Cmeso single bond at 298 K in fluid solution but not at 77 K in a glass matrix, whereas the acceptors have very limited motion as they are blocked by β-methyl groups. This case is interesting because all the structural and spectroscopic parameters affecting the rate for singlet energy transfer according to a Förster Resonance Energy Transfer are only weakly temperature dependent, leaving only the Dexter mechanism explaining the larger variation in rate of energy transfers with the temperature h…
Front Cover: Modelling Photoionisation in Isocytosine: Potential Formation of Longer‐Lived Excited State Cations in its Keto Form (ChemPhysChem 21/20…
2021
Quantum Chemistry of Excited States in Polyhedral Boranes
2015
In this Chapter we describe the electronic structure of ground states and excited states of the two isomers of octadecaborane (22), anti- and syn-B18H22, and the new derivative of anti-B18H22, the polyhedral substituted borane 4,4′-(HS)2-anti-B18H20. A theoretical interpretation is given on the fluorescence of the anti-B18H22 isomer, and the non-radiative decay of the syn-B18H22 isomer, an unsolved problem since 1962. For the new derivative of anti-B18H22, substitution of hydrogen atoms in positions 4 and 4′ by SH groups allows the tuning of the photophysical properties in 4,4′-(HS)2-anti-B18H20, facilitating intersystem crossing from the excited singlet state to the triplet state.