Impact of isoelectronic substitution on the excited state processes in polycyclic aromatic hydrocarbons: a joint experimental and theoretical study of 4a,8a-azaboranaphthalene.

Substituting CC with the isoelectronic BN units is a promising approach to modify the optoelectronic properties of polycyclic aromatic hydrocarbons. While computational studies have already addressed trends in the electronic structure of the various isosteres, experimental data are still scarce. Here, the excited state spectroscopy and dynamics of 4a,8a-azaboranaphthalene were studied by picosecond time-resolved photoionization in a supersonic jet and analyzed with the aid of XMS-CASPT2 and time-dependent DFT calculations. A resonance-enhanced multiphoton ionization spectrum (REMPI) reveals the S1 origin at  = 33 830 ± 12 cm-1. Several vibrational bands were resolved and assigned by comparison with the computations. A [1+1] photoelectron spectrum via the S1 origin yielded an adiabatic ionization energy of 8.27 eV. Selected vibrational bands were subsequently investigated by pump-probe photoionization. While the origin as well as several low-lying vibronic states exhibit lifetimes in the ns-range, a monoexponential decay is observed at higher excitation energies, ranging from 400 ps at +1710 cm-1 to 13 ps at +3360 cm-1. The deactivation is attributed to an internal conversion of the optically excited S1 state via a barrier that gives access to a conical intersection (CI) to the S0 state. The doping significantly changes the energetic ordering of CIs and lowers the corresponding energy barrier for the associated deactivation pathway, as revealed by nudged elastic band (NEB) calculations.

Non-Radiative Deactivation in Isolated Quinoline.

The photophysics of the S2 1(ππ*) state of the polycyclic aromatic nitrogen-containing hydrocarbon (PANH) quinoline is investigated in a free jet using a picosecond laser system. A [1 + 1] multiphoton ionization spectrum yields the S2 origin at around 32 200 cm-1 and reveals several vibronic bands. In time-resolved experiments, quinoline is then excited between 312.2 and 279.7 nm. Probe wavelengths of 351 and 263.5 nm are employed. The dynamics is monitored by time-resolved photoelectron imaging. The images reveal a short-lived band at high electron kinetic energies with a ps lifetime and a band at lower electron kinetic energies that shows an offset at long delay times. In comparison with previous work, the offset is assigned to ionization from the T1 state. Lifetimes decrease from 45 ps at the S2 origin to 11 ps at +3550 cm-1. Most likely, the S2 1(ππ*) state deactivates by internal conversion to the S1 1(nπ*) state, followed by intersystem crossing to the triplet manifold.

IR/UV Double Resonance Study of the 2-Phenylallyl Radical and its Pyrolysis Products.

Isolated 2-phenylallyl radicals (2-PA), generated by pyrolysis from a nitrite precursor, have been investigated by IR/UV ion dip spectroscopy using free electron laser radiation. 2-PA is a resonance-stabilized radical that is considered to be involved in the formation of polycyclic aromatic hydrocarbons (PAH) in combustion, but also in interstellar space. The radical is identified based on its gas-phase IR spectrum. Furthermore, a number of bimolecular reaction products are identified, showing that the self-reaction as well as reactions with unimolecular decomposition products of 2-PA form several PAH efficiently. Possible mechanisms are discussed and the chemistry of 2-PA is compared with the one of the related 2-methylallyl and phenylpropargyl radicals.

Time-resolved photoelectron spectroscopy of 4-(dimethylamino)benzethyne - an experimental and computational study.

We investigated the excited-state dynamics of 4-(dimethylamino)benzethyne (4-DMABE) in a combined theoretical and experimental study using surface-hopping simulations and time-resolved ionisation experiments. The simulations predict a decay of the initially excited S2 state into the S1 state in only a few femtoseconds, inducing a subsequent partial twist of the dimethylamino group within ∼100 fs. This leads to drastically reduced Franck-Condon factors for the ionisation transition to the cationic ground state, thus inhibiting the effective ionisation of the molecule, which leads to a vanishing photoelectron signal on a similar timescale as observed in our time-resolved photoelectron spectra. From the phototoelectron spectra, an adiabatic ionisation energy of 7.17 ± 0.02 eV was determined. The experimental decays match the theoretical predictions very well and the combination of both reveals the electronic characteristics of the molecule, namely the role of intramolecular charge transfer (ICT) states in the deactivation pathway of electronically excited 4-DMABE.

Stacking Is Favored over Hydrogen Bonding in Azaphenanthrene Dimers.

N-Doped polycyclic aromatic hydrocarbons have recently emerged as potential organic electronic materials. The function of such materials is determined not only by the intrinsic electronic properties of individual molecules but also by their supramolecular interactions in the solid state. Therefore, a proper characterization of the interactions between the individual units is of interest to materials science since they ultimately govern properties such as excitons and charge transfer. Here, we report a joint experimental and computational study of two azaphenanthrene dimers to determine the structure and the nature of supramolecular interactions in the aggregates. IR/UV double-resonance experiments were carried out using far- and mid-infrared free-electron laser radiation. The experimental spectra are compared with quantum chemical calculations for the lowest-energy π-stacked and hydrogen-bonded structures. The data reveal a preference of the π-stacked structure for the benzo[f]quinoline and the phenanthridine dimer.