ABSTRACT
The photophysical properties of three 3-diethylphosphonocoumarin derivatives are studied by transient absorption spectroscopy and DFT calculations. The measured lifetime of the first excited singlet state changes upon halogen substitution at the 6-position from 40 ps for the unsubstituted compound to 100 ps for Cl and 24 ps for Br. This observation is in clear contradiction with the estimated singlet-triplet quantum yield, which increases with atomic weight of the substituted atom and is usually referred as a heavy-atom effect. The DFT calculations give evidence that the main reason for this behavior is the different composition of the HOMO, while the LUMO is similar for all three compounds. The optical excitation leads to intramolecular charge transfer from the halogen lone pairs to the π* molecular orbital and thus to a significant change in the molecular dipole moment. Hence, the latter phenomenon in combination with the heavy-atom effect enables an independent control of singlet lifetime and singlet-triplet quantum yield in the studied 3-diethylphosphonocoumarin derivatives.
ABSTRACT
[This corrects the article DOI: 10.1039/D0RA05737A.].
ABSTRACT
We demonstrate a single-stage, multipass Ti:sapphire amplifier capable of delivering sub-13 fs, 3.2 mJ pulses at a 1 kHz repetition rate. Gaussian filters are used to suppress the gain-narrowing effect, thereby enabling the achievement of an ultrabroadband flat-top spectrum with a FWHM>130 nm. The carrier-envelope phase (CEP) of the output pulses is actively stabilized via the feed-forward scheme (for the oscillator) and a fast 1 kHz f-to-2f interferometer, which corrects the amplifier-induced CEP drift. The single-shot 75 h CEP measurement yielded rms noise of <150 mrad.
