The appearance of surface-induced phases of molecular crystals is a frequently observed phenomenon in organic electronics. However, despite their fundamental importance, the origin of such phases is not yet fully resolved. The organic molecule 6,6'-dibromoindigo (Tyrian purple) forms two polymorphs within thin films. At growth temperatures of 150 °C, the well-known bulk structure forms, while at a substrate temperature of 50 °C, a surface-induced phase is observed instead. In the present work, the crystal structure of the surface-induced polymorph is solved by a combined experimental and theoretical approach using grazing incidence X-ray diffraction and molecular dynamics simulations. A comparison of both phases reveals that π-π stacking and hydrogen bonds are common motifs for the intermolecular packing. In-situ temperature studies reveal a phase transition from the surface-induced phase to the bulk phase at a temperature of 210 °C; the irreversibility of the transition indicates that the surface-induced phase is metastable. The crystallization behavior is investigated ex-situ starting from the sub-monolayer regime up to a nominal thickness of 9 nm using two different silicon oxide surfaces; island formation is observed together with a slight variation of the crystal structure. This work shows that surface-induced phases not only appear for compounds with weak, isotropic van der Waals bonds, but also for molecules exhibiting strong and highly directional hydrogen bonds.

Department of Condensed Matter Physics Charles University Prague Ke Karlovu 5 Prague 12116 2 Czech Republic

Department of Physics Humboldt Universität zu Berlin Brook Taylor Straße 6 12489 Berlin Germany

Institute of Semiconductor and Solid State Physics Johannes Kepler University Linz Altenbergerstraße 69 4040 Linz Austria; National Center for Physics Quaid e Azam University Campus Islamabad Pakistan

Institute of Solid State Physics NAWI Graz Graz University of Technology Petersgasse 16 8010 Graz Austria

Institute of Solid State Physics NAWI Graz Graz University of Technology Petersgasse 16 8010 Graz Austria; Division of Neuroradiology Medical University of Graz Auenbruggerplatz 9 8036 Graz Austria

Institute of Solid State Physics NAWI Graz Graz University of Technology Petersgasse 16 8010 Graz Austria; Institute of Pharmaceutical Sciences Department of Pharmaceutical Technology University of Graz Universitätsplatz 1 8010 Graz Austria

Institute of Solid State Physics University of Bremen Otto Hahn Allee 1 28359 Bremen Germany; Institute of Semiconductor and Solid State Physics Johannes Kepler University Linz Altenbergerstraße 69 4040 Linz Austria

Physical Chemistry Johannes Kepler University Linz Altenbergerstraße 69 4040 Linz Austria

School of Chemistry University of Southampton Southampton SO17 1BJ United Kingdom; Dipartimento di Chimica Industriale Toso Montanari Università di Bologna viale Risorgimento 4 40136 Bologna Italy

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