By measuring its IR phosphorescence the formation of singlet molecular oxygen 1 O 2 photosensitized by rhodamine dyes is directly proved. The 1 O 2 formation rate is compared with that expected from the low probability (≈1%) of intersystem crossing of the photosensitizers. The quantum yield for triplet population and the triplet lifetime of the investigated dyes is measured by using a laser-scanning-microscopy technique. The influence of quenching agents (nitrobenzene and COT) is discussed. It results that the formation of 1 O 2 can be prevented effectively by quenching of the S 1 or T state of the photosensitizer. The influence of the molecular ground-state oxygen 3 O 2 concentration [ 3 O 2 ] is investigated. The presence of the paramagnetic 3 O 2 leads to an increased S 1 →T intersystem crossing rate of the photosensitizers and therefore to a reinforced formation of singlet molecular oxygen. It is found for rhodamine 6G as well as for rose bengal that in air-saturated acetonitrile nearly the half of the excited dye triplets are quenched by molecular oxygen. The 1 O 2 concentration can be significantly reduced by decreasing the 3 O 2 concentration below its air saturated level.
We report the first realization of a cw solid-state dye laser. The laser medium consists of a laser dye (Rhodamine 6G) dissolved in a photopolymer. The UV-cured solution is sandwiched between two DVD substrates. The resonator design was derived from a conventional liquid solvent dye laser geometry. The laser radiation can be tuned from 565 to 615 nm by using a birefringent filter. A pump power of 2 W leads to a cw output power of more than 20 mW.
Homoleptic and heteroleptic ruthenium trisphenanthrolines were prepared with azacrown ethers attached to the 4,7-positions of the phenanthrolines to maximise the electronic communication between the ruthenium and the crown ethers as complexation sites. Redox and spectral data were processed to explain the non-steady trends in the absorption and emission spectra in the series. Addition of Ba2+ entailed large shifts in the redox potential (up to 370 mV) and in the emission spectra (up to 87 nm). Due to the crowded situation of the azacrown ether units in, this complex showed a non-linear behaviour both in the redox and emission properties upon loading with Ba2+ that is postulated to originate from the intermediate formation of sandwich type complexes.
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