Solving the Puzzle of Unusual Excited-State Proton Transfer in 2,5-Bis(6-methyl-2-benzoxazolyl)phenol.

2,5-Bis(6-methyl-2-benzoxazolyl)phenol (BMP) exhibits an ultrafast excited-state intramolecular proton transfer (ESIPT) when isolated in supersonic jets, whereas in condensed phases the phototautomerization is orders of magnitude slower. This unusual situation leads to nontypical photophysical characteristics: dual fluorescence is observed for BMP in solution, whereas only a single emission, originating from the phototautomer, is detected for the ultracold isolated molecules. In order to understand the completely different behavior in the two regimes, detailed photophysical studies have been carried out. Kinetic and thermodynamic parameters of ESIPT were determined from stationary and transient picosecond absorption and emission for BMP in different solvents in a broad temperature range. These studies were combined with time-dependent- density functional theory quantum-chemical modeling. The excited-state double-well potential for BMP and its methyl-free analogue were calculated by applying different hybrid functionals and compared with the results obtained for another proton-transferring molecule, 2,5-bis(5-ethyl-2-benzoxazolyl)hydroquinone (DE-BBHQ). The results lead to the model that explains the difference in proton-transfer properties of BMP in vacuum and in the condensed phase by inversion of the two lowest singlet states occurring along the PT coordinate.

Electron transfer across a spiro link: extreme solvatofluorochromism of a compact spiro-bridged N,N-dimethylaniline-phthalide dyad.

Intramolecular electron transfer over the sp3-C-link in dimethyl-aniline-spiro-phthalide leads to extreme solvatofluorochromism (11 600 cm-1) and a fluorescence maximum shift from 357 (hexane) to 595 nm (acetonitrile). The spiro link enhances π-σ* negative hyperconjugation leading to C-O bond elongation and electron transfer over a longer distance than in a non-spirocyclic analogue.

Low-temperature spectra of the analogues of 10-hydroxybenzo[h]quinoline as an indication of barrierless ESIPT.

The absorption and fluorescence spectra of two analogues of 10-hydroxybenzo[h]quinoline (10-HBQ), namely, 1-hydroxy-7-methylbenzo[c]acridine (HMBA) and 4-hydroxybenzo[c]phenanthridine (HBPA), were studied in n-alkane matrices at 5 K. Considerable energy separation between the onsets of the spectra and broadening of the bands was an indication that intramolecular proton transfer (ESIPT) takes place at such a low temperature. DFT and ab initio methods were used to calculate the electronic transition energies and oscillator strengths and the vibronic structure of the electronic spectra. Shortcomings in our knowledge of the shape of the potential energy surface for ESIPT systems are highlighted in the context of the discussion of the shape of the electronic spectra. The π-expansion of the 10-HBQ chromophore achieved by adding a benzene moiety at various positions adjacent to the pyridine ring led to compounds possessing diverse photophysical properties, ranging from the non-ESIPT strongly fluorescent molecule of 10-hydroxy-1-azaperylene to weakly emitting (or nonemitting) molecules, where ESIPT occurs very efficiently.

12-hydroxy-1-azaperylene-limiting case of the ESIPT system: enol-keto tautomerization in S0 and S1 states.

Absorption, fluorescence, and fluorescence excitation spectra of 12-hydroxy-1-azaperylene (HAP) and 1-azaperylene were studied in n-alkane matrices at 5 K. Two stable tautomers of HAP, each of them in n-nonane embedded in two sites, were identified and attributed to the enol and keto forms. Theoretical calculations of the energy and vibrational structure of the spectra suggest that tautomer A, with the (0, 0) transition energy at 18,980 ± 10 cm(-1) (and 19,060 ± 10 cm(-1) in the high energy site), should be identified as the keto form, whereas tautomer B, with the (0, 0) energy at 19,200 ± 20 cm(-1) (19,290 ± 20 cm(-1)), as the enol form. Observation of absorption and fluorescence of both tautomeric forms and lack of large Stokes shift of fluorescence of the keto form classify HAP as the limiting case of the excited-state intramolecular proton transfer system.

Single dibenzoterrylene molecules in naphthalene and 2,3-dimethylnaphthalene crystals: vibronic spectra.

Fluorescence excitation spectra of single dibenzoterrylene (DBT) molecules embedded in naphthalene (N) and 2,3-dimethylnaphthalene (2,3-DMN) crystals were studied at 5 K. The frequencies characterizing the vibronic structure of single DBT molecules in an N crystal agree with the theoretical prediction for the isolated DBT molecule. The 'dipolar' disorder encountered in 2,3-DMN crystals leads to a broad distribution of frequencies of the (0,0) lines of single DBT molecules. Moreover, the observed vibronic frequencies and intensities in the spectrum of DBT in 2,3-DMN crystals are slightly different to those in an N crystal. We conclude that the structure of DBT molecules in a 2,3-DMN crystal is disturbed in comparison with isolated DBT and the main change concerns its central tetracene moiety.