Dynamics of excited state proton transfer in nitro substituted 10-hydroxybenzo[h]quinolines.

The ground state tautomerism and excited state intramolecular proton transfer (ESIPT) of 10-hydroxybenzo[h]quinoline (HBQ) and its nitro derivatives, 7-nitrobenzo[h]quinolin-10-ol (2) and 7,9-dinitrobenzo[h]quinolin-10-ol (3), have been studied in acetonitrile using steady state as well as time dependent spectroscopy and quantum-chemical calculations. In addition to the enol form absorbance in the range 360-390 nm, the absorption spectra of 2 and 3 exhibit a red shifted band at ∼450 nm. Chemometric data processing, based on individual band decomposition, allowed us to estimate the position of the ground state enol-keto tautomeric equilibrium (ΔG values of 1.03 and 0.62 kcal mol-1 respectively for 2 and 3). The fluorescence stems from the keto form even if the enol form is optically excited as proven by the shape of the excitation spectra indicating that ESIPT takes place. The Stokes shift of the substituted compounds is substantially lower compared to HBQ, which follows from the fact that the substitution occurs in the formal cyclohexa-2,4-dienone moiety and leads to a decrease of the HOMO level of the keto tautomer. The pump-probe experiments show that in the nitro substituted HBQs 2 and 3 ESIPT occurs with a time constant of 0.89 ps and 0.68 ps, respectively. In both cases a mixture of the enol and proton transfer forms is optically excited. The enol form exhibits then the ESIPT and subsequently both fractions take the same relaxation path. We propose that in 2 and 3 the ESIPT path exhibits a potential energy barrier resulting in an incoherent rate governed process while in HBQ the ESIPT proceeds as a ballistic wavepacket motion along a path without significant barriers. The theoretical calculations (M06-2X/TZVP) confirm the existence of a barrier in the ground and excited states as result of the substitution.

Solvent control of intramolecular proton transfer: is 4-hydroxy-3-(piperidin-1-ylmethyl)-1-naphthaldehyde a proton crane?

The solvent dependent excited state dynamics of 4-hydroxy-3-(piperidin-1-ylmethyl)-1-naphthaldehyde (compound 2), a candidate for a molecular switch based on intramolecular proton transfer, was investigated by ultrafast spectroscopy and quantum-chemical calculations. In acetonitrile a mixture of molecules in the enol and zwitterionic proton transfer (PT) form exists in the ground state. However, the zwitterion is the energetically favored one in the electronically excited state. Optical excitation of the enol form results in intramolecular proton transfer and formation of the PT form within 1.4 ps. In addition we observe the appearance of a long living species with a rate of 1/(330 ps) which returns to the original ground state on time scales beyond 2 ns and which is attributed to the triplet state. In toluene the enol form is the only observed ground state tautomer, but no light induced proton transfer occurs. Again the long living triplet state is formed, even with a faster rate of 1/(11 ps). In methanol hydrogen bonds between 2 and solvent molecules stabilize strongly the PT form in the ground as well as in the excited state. Also in this case no light induced intramolecular proton transfer was observed but the formation of a long living species was. However, its absorption spectrum is distinctly different from the triplet state seen in acetonitrile and methanol.

4-Hydroxy-1-naphthaldehydes: proton transfer or deprotonation.

A series of naphthaldehydes, including a Mannich base, have been investigated by UV-Vis spectroscopy, NMR and theoretical methods to explore their potential tautomerism. In the case of 4-hydroxy-1-naphthaldehyde concentration dependent deprotonation has been detected in methanol and acetonitrile. For 4-hydroxy-3-(piperidin-1-ylmethyl)-1-naphthaldehyde (a Mannich base) an intramolecular proton transfer involving the OH group and the piperidine nitrogen occurs. In acetonitrile the equilibrium is predominantly at the OH-form, whereas in methanol the proton transferred tautomer is the preferred form. In chloroform and toluene, the OH form is completely dominant. Both 4-hydroxy-1-naphthaldehyde and 4-methoxy-1-naphthaldehyde (fixed enol form) show dimerization in the investigated solvents and the crystallographic data, obtained for the latter, confirm the existence of a cyclic dimer.

Quantification of grafted poly(ethylene glycol)-silanes on silicon by time-of-flight secondary ion mass spectrometry.

Silicon grafted monodisperse poly(ethylene glycol) (PEG) silanes with various PEG chain lengths and mixtures of these were systematically analyzed with static time-of-flight secondary ion mass spectrometry (TOF-SIMS). The mass spectra show differences in the various relative signal intensities, an observation that was used to elucidate important aspects of the grafting process. The relationship between PEG-silane fragment ion abundances and Si(+) ion abundances were used to (i) qualitatively describe layer thicknesses of grafted mixtures of PEG-silanes on silicon, (ii) construct a calibration curve from which PEG chain length (or molecular mass) can be determined and (iii) quantitatively determine surface mixture compositions of grafted monodisperse PEG-silanes of different chain lengths (3, 7 and 11 PEG units). The results suggest that discrimination does take place in the adsorption process. The PEG-silane with the shorter PEG chain is discriminated for mixtures containing PEG3-silane, whereas the PEG-silane with the longer PEG chain is discriminated in PEG7/PEG11-silane mixtures. The origin of this difference in adsorption behavior is not well understood. Aspects of the grafting process and the TOF-SIMS analyses are discussed.