Search results for "Triplet"

Aromatic Ketones as Photocatalysts: Combined Action as Triplet Photosensitiser and Ground State Electron Acceptor

2006

Transformation of monuron photosensitized by soil extracted humic substances: energy or hydrogen transfer mechanism?

1997

The humic and fulvic acids extracted from a Ranker type soil sensitize the transformation of monuron. When monuron is irradiated at 365 nm in the presence of the fulvic acid, its degradation is faster in deoxygenated medium than in air-saturated solution. Chloride ions are released, and the para-hydroxylated derivative is formed as upon direct photolysis. It is deduced that the consumption of monuron observed in the absence of oxygen is due to an energy transfer from reactive triplet states of the fulvic acid to monuron. Energy transfer reactions also take place when hydroquinone or acetophenone are used as sensitizers, showing that the energy level of the triplet state of monuron is lower …

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…

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…

A tetramethoxybenzophenone as efficient triplet photocatalyst for the transformation of diazo compounds.

2007

The aromatic ketone 2,2',4,4'-tetramethoxybenzophenone has a strong absorption band between 300 and 375 nm, and its pi,pi* triplet excited-state is selectively populated in methanol. Both facts make this aromatic ketone a versatile and efficient triplet photocatalyst for the transformation of alpha-diazo carbonyl compounds into mainly the cyclopropanation product.

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.

Singlet oxygen generation in PUVA therapy studied using electronic structure calculations

2009

Abstract The ability of furocoumarins to participate in the PUVA (Psoralen + UV-A) therapy against skin disorders and some types of cancer, is analyzed on quantum chemical grounds. The efficiency of the process relies on its capability to populate its lowest triplet excited state, and then either form adducts with thymine which interfere DNA replication or transfer its energy, generating singlet molecular oxygen damaging the cell membrane in photoactivated tissues. By determining the spin–orbit couplings, shown to be the key property, in the intersystem crossing yielding the triplet state of the furocoumarin, the electronic couplings in the triplet–triplet energy transfer process producing …

Oxygen, Its Nature and Chemistry: What Is so Special About This Element?

2010

It would seem that an introduction to oxygen is unnecessary, for we deal with it and depend upon it every moment of our lives. Oxygen is to us the essential stuff of the air we breathe. We are aerobic animals who obtain energy by oxidizing foodstuffs. As such, we are wholly dependent on oxygen for life – go without it for a couple of minutes and we panic and may even suffer irreversible brain damage. In a few more minutes, we perish. Animal metabolism depends upon oxygen for almost all of its energy-generating processes. Yet this was not always so. Early in the history of the Earth, there was essentially no free oxygen anywhere, although oxygen has always been one of the most abundant eleme…

Through-bond versus through-space T1 energy transfers in organometallic compound-metalloporphyrin pigments

2009

The preparation and characterization of two d9−d9 M2-bonded Pt2(dppm)2(C≡CC6H4-M(P))2 complexes (where M = Zn or Pd, and P = diethylhexamethylporphyrin) were achieved. The central [Pt2(dppm)2(C≡CC6H4)2] organometallic unit appears to be an independent chromophore and is suspected to be luminescent at 77 K (in 2MeTHF) in the porphyrin-containing complexes, as this is the case for the unfunctionalized Pt2(dppm)2(C≡CPh)2 parent compound. However, when this spacer is connected (by a single C−C bond) to either M(P) (M = Zn, Pd), even in the absence of conjugation (as the computed dihedral angle between the C6H4 and porphyrin planes is ∼84.5°), total quenching of the luminescence of the [Pt2(dppm…

Quantum chemical study on the population of the lowest triplet state of psoralen

2007

Abstract The efficient population of the low-lying triplet ππ * state of psoralen is studied with the quantum chemical CASPT2 method. Minima, singlet–triplet crossings, conical intersections, and reaction paths on the low-lying singlet and triplet states hypersurfaces of the system have been computed together with electronic energy gaps and spin–orbit coupling terms. A mechanism is proposed, favorable in the gas phase, for efficient deactivation of the initially populated singlet excited ππ * state, starting with an intersystem crossing with an n π * triplet state and evolving via a conical intersection toward the final lowest-lying ππ * triplet state, protagonist of the reactivity of psora…