The absence of a central metal ion destabilizes phthalocyanine on In$_2$O$_3$(111)

Abstract: Metal phthalocyanines (MPc) are a versatile molecular platform for applications ranging from organic optoelectronic devices to single-atom catalysis (SAC). Their adsorption and layer formation on the prototypical transparent electrode substrates of organic optoelectronic devices is directly relevant for charge injection and transport across the organic-oxide interface. Moreover, the well-defined M-N$_4$ coordination of the metal cation defines their activity as SACs for (electro-)catalysis. Here, the adsorption of the metal-free phthalocyanine (H$_2$Pc) is characterized on In$_2$O$_3$(111) using low-temperature STM, nc-AFM, and STS. In$_2$O$_3$ is not only a model system of indium tin oxide (ITO) but also an active catalytic material for CO$_2$ reduction. H$_2$Pc adsorbs in the same site and configuration reported for copper phthalocyanine [J. Mater. Chem. C 13, 17650-17661 (2025)] and for the majority of cobalt phthalocyanine [Surf. Sci. 722, 122065 (2022)]. Despite this shared preference in adsorption site, H$_2$Pc cannot be organized into extended and ordered monolayer structures by gentle annealing: the molecule starts to decompose at $\approx$50$<sup>\circ$C, well below the temperature used to grow monolayers of CoPc and CuPc. Self-metalation is not observed on stoichiometric In$_2$O$_3$(111). On the reduced surface where In$<sup>0$ adatoms are present, new H$_2$Pc-related features appear but cannot be identified by imaging only. The comparison of H$_2$Pc with CoPc and CuPc identifies distinct roles of the central metal ion in the metal-Pc/In$_2$O$_3$(111) systems: it acts as a structural anchor that stabilizes the macrocycle against decomposition on the surface, and it modifies the frontier-orbital character in ways that determine whether a second adsorption configuration is populated.