Fluorescence Excitation and Dispersed Fluorescence Spectra of the 1-Hydronaphthyl Radical (1-C10H9) in Solid para-Hydrogen.

Matrix isolation spectroscopy with para-hydrogen (p-H2) has previously been employed to record IR absorption spectra of hydrogenated and protonated polycyclic aromatic hydrocarbons (PAHs), prospective carriers of unidentified infrared and diffuse interstellar bands. Despite the promising prospects of p-H2 as matrix host, especially the rather weak interaction with the guest molecules and the resulting small matrix shifts, p-H2 matrix isolation spectroscopy has rarely been applied to study electronic transitions of guest molecules. Here, we present the dispersed fluorescence and fluorescence excitation spectrum of the 1-hydronaphthyl radical (1-C10H9) isolated in solid p-H2. We observed a strong 000 band associated with the electronic transition to the first excited electronic state at 18881 cm-1, red-shifted by ∼68 cm-1 relative to a value reported for jet-cooled 1-C10H9. From a comparison of our experimental results to simulated vibrationally resolved electronic absorption and emission spectra computed on the basis of (TD-)DFT geometry optimizations and scaled harmonic vibration calculations using the FCclasses code, we derived assignments for observed vibronic transitions. The dispersed fluorescence spectrum of 1-C10H9 is new; it complements the infrared spectrum and identified many vibrational modes unidentifiable with infrared. The excitation spectrum covers a much wider spectral range than previous reports. We compare the excitation spectrum in solid p-H2 to the reported electronic absorption spectrum of jet-cooled gaseous 1-C10H9 and that of 1-C10H9 isolated in solid Ne to assess the influence of p-H2 as a matrix host on the electronic transition of 1-C10H9 and discuss a potential contribution of 1-C10H9 to the diffuse interstellar bands.

IR-VUV spectroscopy of pyridine dimers, trimers and pyridine-ammonia complexes in a supersonic jet.

The infrared spectra of the C-H stretching vibrations of (pyridine)m, m = 1-3, and the N-H stretching vibrations of (pyridine)m-(NH3)n, m = 1, 2; n = 1-4, complexes were investigated by infrared (IR)-vacuum ultraviolet (VUV) spectroscopy under jet-cooled conditions. The ionization potential (IP0) of the pyridine monomer was determined to be 74 546 cm-1 (9.242 eV), while its complexes showed only smooth curves of the ionization thresholds at ∼9 eV, indicating large structural changes in the ionic form. The pyridine monomer exhibits five main features with several satellite bands in the C-H stretching region at 3000-3200 cm-1. Anharmonic calculations including Fermi-resonance were carried out to analyze the candidates of the overtone and combination bands which can couple to the C-H stretching fundamentals. For (pyridine)2 and (pyridine)3, most C-H bands are blue-shifted by 3-5 cm-1 from those of the monomer. The structures revealed by random searching algorithms with density functional methods indicate that the π-stacked structure is most stable for (pyridine)2, while (pyridine)3 prefers the structures stabilized by dipole-dipole and C-Hπ interactions. For the (pyridine)m-(NH3)n complexes, the mass spectrum exhibited a wide range distribution of the complexes. The observed IR spectra in the N-H stretching vibrations of the complexes showed four main bands in the 3200-3450 cm-1 region. These features are very similar to those of (NH3)n complexes, and the bands are assigned to the anti-symmetric N-H stretching band (ν3), the symmetric N-H stretching (ν1) band, and the first overtone bands of the N-H bending vibrations (2ν4). The anharmonic calculations including the Fermi-resonance between ν1 and 2ν4 well reproduced the observed spectra.

Strong Hydrogen Bonding with Inorganic Pendant Polyhedral Oligomeric Silsesquioxane Nanoparticles Provides High Glass Transition Temperature Poly(methyl methacrylate) Copolymers.

We report a series of poly(methyl methacrylate) (PMMA) copolymers containing small amounts of methacrylamide (MAAM) and pendant polyhedral oligomeric silsesquioxane (POSS) methyl acrylate (MAPOSS) segments. The hydrogen bonding interactions of the MAAM monomer units and the inorganic POSS nanoparticle units improved the thermal and mechanical properties of the PMMA copolymers. For example, PMMA copolymerization with 5 wt% PMAAM and 5 wt% PMAPOSS monomers could enhance the glass transition temperature to 142°C, with higher modulus, higher water contact angle, and reasonably high transparency. Such copolymers have potential to replace PMMA homopolymers in optical applications.

Ternary polybenzoxazine/POSS/SWCNT hybrid nanocomposites stabilized through supramolecular interactions.

In this study we linked zero-dimensional polyhedral oligomeric silsesquioxane (POSS) with one-dimensional single-walled carbon nanotubes (SWCNTs) as dual-dimensional nanohybrid complexes within polybenzoxazine matrices, stabilized through noncovalent supramolecular interactions. First, we synthesized a new bifunctionalized benzoxazine (Py-Bz-T), presenting thymine (T) and pyrene (Py) units, that displayed excellent thermal properties after thermal curing, because its T moieties increased the physical cross-linking density. Second, we prepared Py-Bz-T/OBA-POSS [octuply adenine (A)-functionalized POSS] nanocomposites and investigated, using nuclear magnetic resonance and Fourier transform infrared spectroscopies, the multiple hydrogen bonding AT interactions between Py-Bz-T and OBA-POSS. Finally, we prepared Py-Bz-T/OBA-POSS/SWCNT ternary hybrid complexes dispersed in THF, stabilized through both multiple hydrogen bonding and π-π stacking interactions. Transmission electron microscopy revealed that the SWCNTs were highly dispersed and covered by the Py-Bz-T/OBA-POSS nanocomposites; these ternary hybrid complexes were stabilized through π-π interactions between Py-Bz-T/OBA-POSS and the SWCNTs, as evidenced using fluorescence spectroscopy.

Symmetry forbidden vibronic spectra and internal conversion in benzene.

The spectra of symmetry-forbidden transitions and internal conversion were investigated in the present work. Temperature dependence was taken into account for the spectra simulation. The vibronic coupling, essential in the two processes, was calculated based on the Herzberg-Teller theory within the Born-Oppenheimer approximation. The approach was employed for the symmetry-forbidden absorption/fluorescence, and internal conversion between 1(1)A(1g) and 1(1)B(2u) states in benzene. Vibrational frequencies, normal coordinates, electronic transition dipole moments, and non-adiabatic coupling matrix elements were obtained by ab initio quantum chemical methods. The main peaks, along with the weak peaks, were in good agreement with the observed ones. The rate constant of the 1(1)A(1g)← 1(1)B(2u) internal conversion was estimated within the order of 10(3) s(-1). This could be regarded as the lower limit (about 4.8 × 10(3) s(-1)) of the internal conversion. It is stressed that the distortion effect was taken into account both in the symmetry-forbidden absorption/fluorescence, and the rate constants of internal conversion in the present work. The distortion effects complicate the spectra and increase the rate constants of internal conversion.