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Polycyclic aromatic hydrocarbons and their nitrogen-substituted analogues are of great interest for various applications in organic electronics. The performance of such devices is determined not only by the properties of the single molecules, but also by the structure of their aggregates, which often form via self-aggregation. Gaining insight into such aggregation processes is a challenging task, but crucial for a fine-tuning of the materials properties. In this work, an efficient approach for the generation and characterisation of aggregates is described, based on matrix-isolation experiments and quantum-chemical calculations. This approach is exemplified for aggregation of acridine. The acridine dimer and trimer are thoroughly analysed on the basis of experimental and calculated UV and IR absorption spectra, which agree well with each other. Thereby a novel structure of the acridine dimer is found, which disagrees with a previously reported one. The calculations also show the changes from excitonic coupling towards orbital interactions between two molecules with decreasing distance to each other. In addition, a structure of the trimer is determined. Finally, an outlook is given on how even higher aggregates can be made accessible through experiment., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

In this work, matrix-isolation spectroscopy and quantum-chemical calculations are used together to analyse the structure and properties of weakly bound dimers of the two isomers benzo[a]acridine and benzo[c]acridine. Our measured experimental electronic absorbance spectra agree with simulated spectra calculated for the equilibrium structures of the dimers in gas-phase, but in contrast, disagree with the simulated spectra calculated for the structures obtained by optimising the experimental solid-state structures. This highlights the sensitivity of the electronic excitations with respect to the dimer structures. The comparison between the solid-state and gas-phase dimers shows how far the intermolecular interactions could change the geometric and electronic structure in a disordered bulk material or at device interfaces, imposing consequences for exciton and charge mobility and other material properties., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

N-Heteropolycycles are among the most promising candidates for applications in organic devices. For this purpose, a profound understanding of the low-energy electronic absorbance and emission characteristics is of crucial importance. Herein, we report high-resolution absorbance and fluorescence spectra of pentacene (PEN) and 6,13-diazapentacene (DAP) in solid neon obtained using the matrix-isolation technique. Accompanying DFT calculations allow the assignment of specific vibrationally resolved signals to corresponding modes. Furthermore, we present for the first time evidence for the formation of van der Waals dimers of both substances. These dimers exhibit significantly different optical characteristics resulting from the change of electronic properties evoked by the incorporation of sp 2 nitrogen into the molecular backbone., (© 2020 The Authors. Published by Wiley-VCH GmbH.)