Excited singlet state kinetics on a subnanosecond time-scale

It is possible to study directly the absorption time-profiles of short-lived excited singlet states by sampling the transient excitation spectra for fluorescence from upper states. This approach has many advantages over direct absorption measurements, since the effects of triplet state absorption can be suppressed and the population time-profiles of excited singlet states can be studied in detail. The first direct measurements are reported of singlet state absorption time profiles in a number of aromatic aza- and carbonyl compounds.     

Excited singlet state absorption spectrum with tunable dye lasers

A technique for measuring absorption from excited states with nanosecond lifetimes utilizing pulsed tunable dye laser probes is described. The method features a simple experimental set-up, and high signal-to-noise ratio. The excited singlet state absorption spectrum of one transition in acridine red is presented.     

One- and two-photon singlet oxygen generation with new fluorene-based photosensitizers.

The spectral properties of new fluorene-based photosensitizers for efficient singlet oxygen production are investigated at room temperature and 77 K. Two-photon absorption (2PA) cross-sections of the fluorene derivatives are measured by the open aperture Z-scan method. The quantum yields of singlet oxygen generation under one- and two-photon excitation (phi(delta) and 2PAphi(delta), respectively), are determined by the direct measurement of singlet oxygen luminescence at approximately 1270 nm. The values of phi(delta) are independent of excitation wavelength, ranging from 0.6-0.9. The singlet oxygen quantum yields under two-photon excitation are 2PAphi(delta) approximately 1/2 phi(delta), indicating that the two processes exhibit the same mechanism of singlet oxygen production, independent of the mechanism of photon absorption.     

Excited state properties of transition metal phosphine complexes

Phosphine ligands determine the excited state properties of a variety of coordination compounds. Phosphines not only influence metal-centered excited states, but participate directly in charge transfer transitions owing to their electron donating and accepting ability. Moreover, intraligand excited states are accessible if the phosphine carries suitable substituents. This diversity is illustrated by selected examples. The excited state behavior is discussed on the basis of spectral (absorption and emission) and photochemical properties of appropriate phosphine complexes.     

Excited state properties of oligophenyl and oligothienyl swivel cruciforms

A comprehensive study has been undertaken of the electronic spectral and photophysical properties of two oligophenyl (BPH and BPHF) and one oligothienyl (BTF) swivel cruciforms involving measurements of absorption, fluorescence, and phosphorescence spectra, quantum yields of fluorescence (phiF), phosphorescence (phiPh) and triplet formation (phiT), lifetimes of fluorescence (tauF) and of the triplet state (tauT), and quantum yields of singlet oxygen production (phiDelta). From these, all radiative kF and radiationless rate constants, kIC and kISC, have been obtained in solution. The energies of the lowest lying singlet and triplet excited states were also determined at 293 K. Several of the above properties have also been obtained at low temperature and in the solid state (thin films). In general, for the phenyl oligophenyl (BPH) and for the oligothienyl (BTF) compounds, the radiationless decay channels (phiIC+phiISC) are the dominant pathway for the excited-state deactivation, whereas with the fluorene based oligophenyl BPHF the radiative route prevails. In contrast to the general rule found for related oligomers (and polymers) where radiative emission from T1 is absent, with the compounds studied, phosphorescence has been observed for all of the compounds, indicating that this type of functionalization can lead to emissive triplets. Time-resolved fluorescence decays with picosecond resolution revealed multiexponential (bi- and triexponential) decay laws compatible with the existence of more than one species or conformation in the excited state. These results are discussed on the basis of conformational flexibility in the excited state.     

Antiviral properties of photosensitizers

Abstract— We have studied the antiviral properties of three different groups of photo-sensitizers, viz. (i) various furyl compounds; (ii) β-carboline alkaloids; (iii) thiophenes and their acetylene derivatives. In general the antiviral potency of the furyl compounds correlated with their ability to produce DNA photoadducts. Among the naturally occurring β-carboline alkaloids, harmine was considerably more potent (in the presence of long wavelength UV radiation, UVA) than several other harmane-related compounds. Slight alterations in chemical structure had profound effects on their antiviral activities. Harmine was shown to inactivate the DNA-virus murine cytomegalovirus (MCMV) by inhibiting viral gene expression, although other targets may also exist. Several eudistomins, carboline derivatives isolated from a tunicate, were also photoactive against viruses. Various plant thiophenes and polyacetylenes were studied in detail. These compounds also required UVA for antiviral activity, and some of them were extremely potent against viruses with membranes, e.g. α-terthienyl, which showed significant activity at only 10^-5μg/ml. When MCMV had been treated with α-terthienyl plus UVA, the virus retained its integrity and penetrated cells normally; but the virus did not replicate. More than 30 additional thiophenes have recently been evaluated, including many synthetic ones, and some of these are even more potent than a-terthienyl. We believe that certain thiophenes possess potential therapeutic value and should be tested against model virus infections in animals.     

Preparation and properties of porphyrin-modified hollow-fiber membranes for use as heterogeneous photosensitizers for singlet oxygen and for artificial photosynthesis

Commercially available cellulose acetate hollow fiber membranes have been modified to incorporate high concentrations of zinc tetraphenylporphyrin (ZnTPP). The modification procedure involves swelling the fibers in a tetrahydrofuran solution saturated with ZnTPP, followed by an aqueous rinse which contracts the fibers and entraps the ZnTPP. The modified membranes are dark purple, containing up to 3% ZnTPP by weight. The membranes remain sufficiently durable to sustain a flow system, and they are impermeable to ionic solutes. The membranes exhibit fluorescence with a short lifetime (<10 nsec) and a spectrum consistent with that of ZnTPP. The membranes are effective as a heterogeneous photosensitizer for the generation of singlet molecular oxygen, monitored by the oxygenation of aqueous 2-furylmethanol. Initial efforts to develop electrontransfer reactions photosensitized by these modified membranes are described. Novel polyether-substituted electron donor and acceptor molecules are effective at increasing photosensitized electron transfer from ZnTPP in nonionic Triton X-100 micelles, but offer only slight success from the ZnTPP-modified membranes.     

Excited state wave functions

Wave functions and energies were calculated for the 2s, 3p ₀, and 4d ₀ states of the hydrogen atom using the Messmer and Rayleigh-Ritz variational methods with minimization of the second eigenvalue. The wave functions were linear expansions of Gaussian functions and both linear and exponential parameters were varied. Except for the two term expansions, calculated values of the energies and expectation values, r ^–1, r and r ² were within two percent of the true values for both methods.     

Excited state tautomerization of azaindole

Fluorescent tryptophan analogs, like azatryptophan, offer an advantage for exploring protein and peptide structure and dynamics. The chromophoric moieties, azaindole, of the azatryptophan analogs are investigated for their potential as fluorescent probes. The photophysical properties of 4-azaindole (4AI) and 5-azaindole (5AI) and their tautomers are characterized through computational and experimental methods. Both 4AI and 5AI undergo excited state tautomerization in the presence of 1 M NaOH. The protonated forms of 4AI and 5AI have a fluorescence emission of 415 and 410 nm, respectively, while the tautomers of 4AI and 5AI have a fluorescent emission of 480 and 450 nm, respectively. Gas phase computations (B3LYP/6-31+G**) show that the N1H azaindole tautomer is lower in energy in the ground state by as much as 12.5 kcal mol(-1), while the N(n)H azaindole tautomer is lower in energy in the excited state by as much as 18.1 kcal mol(-1). Solvent effects on the tautomer energy differences were computed using the isodensity polarized continuum model (IPCM). The polarity of the solvent helps to reduce the energy difference between the tautomers in the ground state by as much as 5.8 kcal mol(-1), but not enough to reverse the ground state tautomer preference.     

New cyclometalated transition-metal based photosensitizers for singlet oxygen generation and photodynamic therapy

The aim of this review article is to introduce recent studies on an emergent class of singlet oxygen photosensitizers of potential applications to the photodynamic therapy,with a primary focus on the cyclometalated transition-metal complexes.Singlet oxygen photosensitization performances of various cyclometalated Ir and Pt scaffolds are reviewed,and the general photophysical properties of relevant systems and the mechanisms of singlet oxygen production via photo-sensitization are also briefly discussed.Thus far,investigations of singlet oxygen sensitization by such Ir and Pt complexes are mainly carried out in organic solvents and under non-physiological conditions,while some research efforts have been made at examining the feasibility of applying pertinent cyclometalated complexes to photodynamic therapy.     

Excited state properties of a new photoinitiating system for laser imaging applications

The design of an efficient photosenzitizer/photoinitiator combination is partly governed by a better understanding of the excited state processes involved. In the present paper, the photochemistry of a thiopyrylium salt (TP) as photosensitizer and of a tetraperester of benzophenone, tetra t-butyl peroxycarbonylbenzophenone (BTTB) as initiator, used in laser imaging applications has been investigated. The reactivity of the triplet states of both compounds BTTB and TP was studied by time-resolved laser absorption spectroscopy. The laser excitation of TP leads to a long-lived triplet state (lifetime 20–25 μsec) and a second species arising from the triplet state which cannot yet be characterized. Under laser excitation, BTTB gives a longlived transient arising from the cleavage of the peroxy bond. The short-lived triplet state cannot be observed on the nanosecond timescale. The triplet state lifetime has been evaluated from quenching experiments and found to be about 1 ns in acetonitrile. The deactivation of the TP triplet state by BTTP was considered, the deactivation constant was found to be equal to 6.6 × 10⁷ m^?1/sec in acetonitrile. The initiation mechanism is discussed.     

Theoretical and experimental analysis of the luminescence signal of singlet oxygen for different photosensitizers

After the generation by different photosensitizers, the direct detection of singlet oxygen is performed by measuring its luminescence at 1270 nm. Using an infrared sensitive photomultiplier, the complete rise and decay time of singlet oxygen luminescence is measured at different concentrations of a photosensitizer, quencher, or oxygen. This allows the extraction of important information about the photosensitized generation of singlet oxygen and its decay, in particular at different oxygen concentrations. Based on theoretical considerations all important relaxation rates and rate constants were determined for the triplet T(1) states of the photosensitizers and for singlet oxygen. In particular, depending on the oxygen or quencher concentration, the rise or the decay time of the luminescence signal exhibit different meanings regarding the lifetime of singlet oxygen or triplet T(1)-state. To compare with theory, singlet oxygen was generated by nine different photosensitizers dissolved in either H2O, D2O or EtOD. When using H2O as solvent, the decaying part of the luminescence signal is frequently not the lifetime of singlet oxygen, in particular at low oxygen concentration. Since cells show low oxygen concentrations, this must have an impact when looking at singlet oxygen detection in vitro or in vivo.     

Excited state properties of sizable molecules in solution: from structure to reactivity

We review some recent advances in quantum mechanical methods devised specifically for the study of excited electronic state of large size molecules in solution. The adopted theoretical/computational framework is rooted in the density functional theory (DFT) and its time-dependent extension (TD-DFT) for the characterization of ground and excited states, in the polarizable continuum model (PCM) for the treatment of bulk solvent effects, and in time-dependent quantum mechanical methods for chemical dynamics. Selected applications to the simulation of absorption spectra, to the interpretation of time-resolved experiments, and to the computation of dissociative electron transfer rates are presented and discussed.     

Second excited singlet state emission spectroscopy of thiocarbonyls. I. Thiophosgene

Well resolved emission spectra have been recorded after dye laser excitation of low-lying vibronic levels in the $\text{B}$(¹A₁) state of Cl₂CS. The effects of substrate pressure, added SF₆ and excitation wavelength on the spectra are reported. A Franck-Condon analysis suggests that the excited state CS bond length is 0.5 Å longer than in the ground state.     

Excited state behaviour of pentahelicene dinitriles

The excited singlet and triplet states 2,13-dicyano[5]helicene (1) and two para-dicyno[5]helicenes containing one and two methyl groups (2 and 3, respectively) were studied in solvents of different polarity as a function of temperature. Fluorescence quenching by electron donors such as triethyl amine indicated photoinduced electron transfer. In the absence of additives triplet states were observed by flash photolysis. The triplet lifetime at room temperature was rather short (<1 μs) and the decay limited by intramolecular processes, e.g. charge transfer in the cases of 2 or 3. Luminescence of singlet molecular oxygen, O₂(¹Δ_g), was observed with moderate and low quantum yield for 1 and 3, respectively. For 1–3, the triplet lifetime increases by six orders of magnitude on going to −196°C. Two subsequently formed triplet states were observed for 3 at lower temperatures. The effects of temperature and solvent polarity on the quantum yields of fluorescence and phosphorescence and the spectroscopic and kinetic triplet absorption properties were examined. The influence of substituents on the deactivation pathways of excited pentahelicenes are discussed.     

Excited state properties of the low-valent bi- and trinuclear complexes of palladium and platinum

A comprehensive review of the excited properties of the low valent (0 and +1) bi- and trinuclear complexes of palladium and platinum is presented. Physical characterization of the nature of the lowest energy excited states along with their photoinduced chemical reactivities toward oxidative additions is discussed.