Photoinduced Electron Transfer in Linear Triarylamine-Photosensitizer-Anthraquinone Triads with Ruthenium(II), Osmium(II), and Iridium(III)

A rigid rod-like organic molecular ensemble comprised of a triarylamine electron donor, a 2,2′-bipyridine (bpy) ligand, and a 9,10-anthraquinone acceptor was synthesized and reacted with suitable metal precursors to yield triads with Ru(bpy)32+, Os(bpy)32+, and [Ir(2-(p-tolyl)pyridine)2(bpy)]+ photosensitizers. Photoexcitation of these triads leads to long-lived charge-separated states (τ = 80–1300 ns) containing a triarylamine cation and an anthraquinone anion, as observed by transient absorption spectroscopy. From a combined electrochemical and optical spectroscopic study, the thermodynamics and kinetics for the individual photoinduced charge-separation and thermal charge-recombination events were determined; in some cases, measurements on suitable donor–sensitizer or sensitizer–acceptor dyads were necessary. In the case of the ruthenium and iridium triads, the fully charge-separated state is formed in nearly quantitative yield

Hydrogen-Bonding Effects on the Formation and Lifetimes of Charge-Separated States in Molecular Triads

Photoinduced electron transfer in two molecular triads comprised of a triarylamine donor, a d6 metal diimine photosensitizer, and a 9,10-anthraquinone acceptor was investigated with particular focus on the influence of hydrogen-bonding solvents on the electron transfer kinetics. Photoexcitation of the ruthenium(II) and osmium(II) sensitizers of these triads leads to charge-separated states containing an oxidized triarylamine unit and a reduced anthraquinone moiety. The kinetics for formation of these charge-separated states were explored by using femtosecond transient absorption spectroscopy. Strong hydrogen bond donors such as hexafluoroisopropanol or trifluoroethanol cause a thermodynamic and kinetic stabilization of these charge-separated states that is attributed to hydrogen bonding between alcoholic solvent and reduced anthraquinone. In the ruthenium triad this effect leads to a lengthening of the lifetime of the charge-separated state from ∼750 ns in dichloromethane to ∼3000 ns in hexafluoroisopropanol while in the osmium triad the respective lifetime increases from ∼50 to ∼2000 ns between the same two solvents. In both triads the lifetime of the charge-separated state correlates with the hydrogen bond donor strength of the solvent but not with the solvent dielectric constant. These findings are relevant in the greater context of solar energy conversion in which one is interested in storing light energy in charge-separated states that are as long-lived as possible. Furthermore they are relevant for understanding proton-coupled electron transfer (PCET) reactivity of electronically excited states at a fundamental level because changes in hydrogen-bonding strength accompanying changes in redox states may be regarded as an attenuated form of PCET

Fluorescence method using labeled chromophores to study the curing kinetics of a polyurethane system

A fluorescence method using labeled chromophores to study the curing kinetics of a polyurethane (PU) system was developed. A PU system based on fluorescent-labeled hexamethylene diisocyanate and a polyol (polyether/polyester) was cured at different temperatures (25, 40, 50, and 65°C). The fluorescent response from the 5-dimethylaminonaphtalene-1-(N-2-aminoethyl)sulfonamide and 4-methacryloylamino-4′-nitrostilbene moieties chemically bonded to the PU system was monitored as a function of the curing time. With the fluorescence data, it was possible to model the kinetics of the curing process. Methods based on the fluorescence intensity ratio and the first moment of the fluorescent band emission were applied to determine the degree of curing of the PU system. In addition, it was possible to calculate an apparent activation energy for the curing process, and a value of 17 kJ/mol was obtained

Poly(β-amino ester)–DNA complexes: Time-resolved fluorescence and cellular transfection studies

A large number of different polymers have been developed and studied for application as DNA carriers for non-viral gene delivery, but the DNA binding properties are not understood. This study describes the efficiency of nanoparticle formation by time-resolved fluorescence measurements for poly(β-amino esters), cationic biodegradable polymers with DNA complexation and transfection capability. From the large library of poly(β-amino esters) ten polymers with different transfection efficacies were chosen for this study. The binding constants for nanoparticle formation were determined and compared to with the same method. Although the DNA binding efficiency of the amine groups are similar for both types of polymers, the overall binding constants are an order of magnitude smaller for poly(β-amino esters) than for 25 kDa polyethylenimines, yet poly(β-amino esters) show comparable DNA transfection efficacy with polyethylenimines. Within this series of polymers the transfection efficacy showed increasing trend in association with relative efficiency of nanoparticle formation.Academy of FinlandNational Institutes of Health (U.S.) (Grant CA132091)National Institutes of Health (U.S.) (Grant CA115527

Exciplex-exciplex energy transfer and annihilation in solid films of porphyrin-fullerene dyads

Exciplex-exciplex annihilation was observed for the first time in porphyrin-fullerene molecular films. The films were prepared using Langmuir-Blodgett and drop casting methods. The exciplex-exciplex interactions were studied using femtosecond pump-probe method. The exciplex-exciplex annihilation can be seen as a fast (within few picoseconds) decay of the transient absorption at excitation densities higher than 0.4 mJ/cm2. Analysis of the excitation density dependences indicates that in average four dyads are involved in the exciplex-exciplex interaction, suggesting that an exciplex-exciplex energy transfer may precede the annihilation

Characterization of thermally aged polyetheretherketone fibres : Mechanical, thermal, rheological and chemical property changes

This paper investigates the effects of thermal degradation on polyetheretherketone (PEEK) fibres. PEEK samples were aged at a constant temperature of 250 °C for 1-128 days and characterized with mechanical tests, FTIR (Fourier Transform Infrared Spectroscopy), DSC (Differential Scanning Calorimetry), rheology, TGA (Thermogravimetric Analysis), SEM (Scanning Electron Microscopy), and UV-Vis diffuse reflectance spectroscopy. The short-term thermal annealing had a positive effect on the mechanical properties, due to the formation and growth of secondary crystals. Crosslinking in the material was verified by rheological inspections. The crosslinking increased the mechanical strength and modulus but reduced the elongation at break of the fibres. FTIR tests showed that carbonyl and hydroxyl groups were slowly formed on the surface of the fibres while ring opening reactions took place. The thermal ageing reduced the thermal stability of PEEK. The decreased stability was observed in the decomposition onset temperature after 8 d and in the melting point and the glass transition temperature after 32 d. The first signs of degradation, crosslinking, embrittlement, and reduced thermal stability, were visible roughly after 8 d of ageing, whereas the deterioration in general usability occurred after 64 d.submittedVersionPeer reviewe

Distributed decay kinetics of charge separated state in solid film

Photoinduced electron transfer in solid films of porphyrin-fullerene dyads was studied using femtosecond pump-probe method. The relaxation of the main photo-product, intramolecular exciplex, was found to be essentially non-exponential. To analyze the decays a model accounting for a distribution of the free or reorganization energies is proposed. The model allows to fit the experimental data using three parameters: non-disturbed time constant, τ0, width of the energy distribution, ΔE, and sensitivity parameter, a = -(Δ G0 + λ0)/2λ0, where ΔG0 and λ0 are the average free and reorganization energies, respectively. The parameters were found to be τ0 = 50 ps, ΔE = 0.09 eV and a = 2 for the exciplex relaxation