Krzysztof Dobek

The measurements of picosecond fluorescence lifetimes with high accuracy and subpicosecond precision

Abstract Systematic studies of the fluorescence picosecond lifetimes determination by laser-excited time-correlated single-photon-counting (TCSPC) have been undertaken. The results have been used to develop methods for determining lifetimes with much smaller error and much greater reproducibility than any hitherto reported. The error in the determination of the lifetimes (±three standard deviations) can be as low as that in simulations and amounts to 0.01 FWHM of the IRF. The lifetimes determined for the second excited singlet state of xanthione in toluene (5.1±0.3 ps ) and in benzene (8.1±0.3 ps ) can be treated as reliable standards of picosecond lifetimes.

Three Modes of Proton Transfer in One Chromophore: Photoinduced Tautomerization in 2‐(1H‐Pyrazol‐5‐yl)Pyridines, Their Dimers and Alcohol Complexes

Studies of 2-(1H-pyrazol-5-yl)pyridine (PPP) and its derivatives 2-(4-methyl-1H-pyrazol-5-yl)pyridine (MPP) and 2-(3-bromo-1H-pyrazol-5-yl)pyridine (BPP) by stationary and time-resolved UV/Vis spectroscopic methods, and quantum chemical computations show that this class of compounds provides a rare example of molecules that exhibit three types of photoreactions: 1) excited-state intramolecular proton transfer (ESIPT) in the syn form of MPP, 2) excited-state intermolecular double-proton transfer (ESDPT) in the dimers of PPP in nonpolar media, as well as 3) solvent-assisted double-proton transfer in hydrogen-bonded 1:1 complexes of PPP and MPP with alcoholic partners. The excited-state processes are manifested by the appearance of a dual luminescence and a bimodal irreversible kinetic coupling of the two fluorescence bands. Ground-state syn-anti equilibria are detected and discussed. The fraction of the higher-energy anti form varies for different derivatives and is strongly dependent on the solvent polarity and hydrogen-bond donor or acceptor abilities.

Influence of Hydrogen Bonds and Nonspecific Interactions on the Spectral and Photophysical Properties of the Excited Singlet States of 4-Aminophthalimide in Amine Solution

The hydrogen-bond and nonspecific interaction energies for 4-aminophthalimide (4-AP), often used as a probe, in the ground electronic and excited singlet states are determined using ab initio computational methods. It is shown that the 4-AP molecule can form three relatively strong hydrogen bonds with trimethylamine (TMA) and triethylamine (TEA), which leads to the formation of S(0)-complexes between the solute and solvent molecules. Only two of the hydrogen bonds with the amine group of 4-AP change significantly their energies upon excitation and deactivation. The theoretical results are necessary to explain the spectral and unusual photophysical properties of 4-AP in amine solutions.

The Influence of Temperature on C153 Steady-State Absorption and Fluorescence Kinetics in Hydrogen Bonding Solvents

In a recent paper (J Fluoresc (2011) 21:1547–1557) a temperature induced modulation of Coumarin 153 (C153) fluorescence lifetime and quantum yield for the probe dissolved in the polar, nonspecifically interacting 1-chloropropane was reported. This modulation was also observed in temperature dependencies of the radiative and nonradiative rates. Here, we show that the modulation is also observed in another 1-chloroalkane—1-chlorohexane, as well as in hydrogen bonding propionitrile, ethanol and trifluoroethanol. Change in the equilibrium distance between S0 an S1 potential energies surfaces was identified as the source of this modulation. This change is driven by temperature changes. It leads to a modulation of the fluorescence transition dipole moment and it is the primary source of the experimental effects observed. Additionally, we have found that proticity of the solvent induces a rise in the fluorescence transition dipole moment, which leads to a shortening of the fluorescence lifetime. Hydrogen bonds are formed by C153 also with hydrogen accepting solvents like propionitrile. We show that while such bonds do not affect the transition probability, they do change the S0 an S1 energy gap which in turn implies a change in non-radiative transition rate in a similar way as in protic solvents, as well as in the fluorescence spectrum position. Finally, the influence of temperature on the energies of hydrogen bonds formed by C153 when acting as hydrogen donor or acceptor is reported.

Temperature influence on the energy of nonspecific and specific interactions taking place between 4-aminophthalimide (4-AP) and homogeneous solvents

Temperature induced spectral shifts of the 4-aminophthalimide (4-AP) emission spectra have been measured and compared to the predictions of the McRae solvent induced shift theory (J. Phys. Chem., 1957, 61, 562-572). Three moderately polar chloroalkanes selected as nonspecifically interacting media, and six hydrogen accepting or/and electron pair donating solvents have been used as the media in which the temperature influence on 4-AP-solvent interactions has been studied in the range of 180-320 K. Using the ab initio determined 4-AP ground state dipole moment and fitting appropriate expression originating from the mentioned theory to the shifts found in the chloroalkanes it has been possible to estimate the 4-AP excited state dipole moment, the probe excited state Onsager radius and its gas phase emission spectrum position. Using these values the thermochromic shifts of 4-AP emission spectra in hydrogen bond forming solvents have been predicted and compared to the experimental one. Temperature has been found to have different impact on the changes, upon excitation of the probe, in the mean values of the energies of different hydrogen bonds formed by 4-AP with solvents molecules.

Deactivation of 6-Aminocoumarin Intramolecular Charge Transfer Excited State through Hydrogen Bonding

This paper presents results of the spectral (absorption and emission) and photophysical study of 6-aminocoumarin (6AC) in various aprotic hydrogen-bond forming solvents. It was established that solvent polarity as well as hydrogen-bonding ability influence solute properties. The hydrogen-bonding interactions between S1-electronic excited solute and solvent molecules were found to facilitate the nonradiative deactivation processes. The energy-gap dependence on radiationless deactivation in aprotic solvents was found to be similar to that in protic solvents.