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.

Hybrid materials comprising ferrocene and diaminoborane moieties: linear concatenation versus macrocyclization.

Combination of borane and diaminoferrocene monomers by Si/B exchange condensation reactions afforded either diazabora-[3]ferrocenophanes or, via stepwise processes, larger macrocycles and a series of linear oligomers. Additional incorporation of p-phenylene moieties in the backbone yielded alternating concatenation.

Linear and macrocyclic oligo(p-phenylene iminoboranes) with ferrocenyl side groups - observation of selective, non-templated macrocyclization.

A series of linear oligo(p-phenylene iminoboranes), which are BN-modified congeners of oligo(p-phenylene vinylenes), featuring pendent ferrocene groups have been prepared. Stoichiometric reaction of a bis-silylamine with a bisborane led to selective formation of an unprecedented macrocycle, without the use of a template.

Poly(ferrocenylene iminoborane): an inorganic-organic hybrid polymer comprising a backbone of moderately interacting ferrocenes.

The first poly(ferrocenylene iminoborane), that is, a polyferrocene-based metallopolymer featuring CC-isoelectronic/-isosteric BN linking units, and a series of monodisperse ferrocenylene iminoborane oligomers are presented. Our studies provide important insight into the structural and electronic nature of this novel class of hybrid materials.