About two decades after extensive studies on anthracene−Ar n clusters in the gas phase, we report corresponding studies in superfluid helium droplets. With AN as a small fluorophore and spectroscopic data from the gas phase and helium droplets, both the formation of clusters and the microsolvation in superfluid helium droplets can be studied. As expected for helium droplets, a significantly higher number of isomeric variants of the respective cluster sizes are obtained, because metastable variants are stabilized by the low temperature and the surrounding helium. Moreover, spectroscopic data recorded in helium droplets reveal cluster configurations with Ar atoms shielded by a helium solvation layer. Surprisingly, AN−Ar n clusters with more than four Ar atoms do not appear to form rigid configurations. The helium droplet data in combination with the gas phase spectra may serve as a suitable reference for further theoretical investigations on solvation and cluster formation in superfluid helium droplets.

Superfluid helium nanodroplets comprised of thousands to millions of helium atoms can serve as a reactor for the synthesis of heterogeneous molecular clusters at cryogenic conditions. The cluster synthesis occurs via consecutive pick-up of the cluster building blocks by the helium droplet and their subsequent coalescence within the droplet. The effective collision cross section of the building blocks is determined by the helium droplet size and thus exceeds by orders of magnitude that of a reactive collision in the gas phase. Moreover, the cryogenic helium environment (at 0.38 K) as a host promotes the formation of metastable cluster configurations. The question arises as to the extent of the actual involvement of the helium environment in the cluster formation. The present study deals with clusters of single phthalocyanine (Pc) molecules with single water molecules. A large fluorophore such as Pc offers several sites where the water molecule can attach. The resulting isomeric variants of the Pc−H 2 O complex can be selectively identified by electronic spectroscopy. We compare the experimental electronic spectra of the Pc− H 2 O complex generated in superfluid helium nanodroplets with the results of quantum-chemical calculations on the same cluster but under gas-phase conditions. The number of isomeric variants observed in the helium droplet experiment comes out the same as that obtained from our gas-phase calculations.