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.

Quantum-State-Sensitive Detection of Alkali Dimers on Helium Nanodroplets by Laser-Induced Coulomb Explosion.

Rubidium dimers residing on the surface of He nanodroplets are doubly ionized by an intense femtosecond laser pulse leading to fragmentation into a pair of Rb^{+} ions. We show that the kinetic energy of the Rb^{+} fragment ions can be used to identify dimers formed in either the X ^{1}Σ_{g}^{+} ground state or in the lowest-lying triplet state, a ^{3}Σ_{u}^{+}. From the experiment, we estimate the abundance ratio of dimers in the a and X states as a function of the mean droplet size and find values between 4∶1 and 5∶1. Our technique applies generally to dimers and trimers of alkali atoms, here also demonstrated for Li_{2}, Na_{2}, and K_{2}, and will enable femtosecond time-resolved measurements of their rotational and vibrational dynamics, possibly with atomic structural resolution.

C2- and C1-Symmetric Configurationally Stable Pyrene-Fused [5]Helicenes Connected via Hexagonal and Heptagonal Rings.

In this paper, we describe the stereospecific synthesis and functional properties of C2- and C1-symmetric pyrene-fused [5]helicene molecules 1 and 2 connected via hexagonal and heptagonal rings, respectively. Both molecules showed high configurational stability and distinct functional properties, which were attributed to the fusing mode of [5]helicene with the pyrene and molecular symmetry. The estimated Gibbs activation energy for enantiomerization of 2 is one of the highest reported values for any π-conjugated molecules incorporating [5]helicene moiety.