Mateo de Doni, Luis ManuelHung, Tzu-ChaoRank, AndreasSpachtholz, RaffaelGiselbrecht, FelixSchön, JonasGross, LeoRepp, JaschaPeña Gil, Diego2026-04-202026-04-202026-03-09Mateo, L. M., Hung, T., Rank, A., Spachtholz, R., Giselbrecht, F., Schön, J., Gross, L., Repp, J., & Peña, D. (2026). Combined In‐Solution and On‐Surface Synthesis of a Fully Fused Cross‐Shaped Phthalocyanine Pentamer. Angewandte Chemie International Edition, 65(11), e21922. https://doi.org/10.1002/anie.2025219221433-7851https://hdl.handle.net/10347/46804Phthalocyanines (Pcs) are a class of technologically relevant tetrapyrrolic macrocycles that offer rich photophysical properties as well as excellent tunability by means of chemical functionalization. Among such functionalization strategies, the synthesis of multinuclear, fully fused Pcs – adjacent macrocycles seamlessly fused through a shared aromatic ring into a continuous π-system – is particularly appealing for the preparation of new, exotic, atomically precise carbon frameworks. However, the notoriously low solubility of Pcs typically impedes the synthesis of oligomers beyond trimers. In addition, the positional control for specific units in large low-symmetry frameworks is particularly challenging. In this work, taking advantage of the benefits of on-surface synthesis under ultra-high vacuum (UHV) conditions, we present a strategy that allows the on-surface synthesis of cross-shaped Pc pentamers. This pentamer, which bears two different metal ions with pre-defined positional control, shows a small transport gap of 1.15 eV on Au(111).eng©2025 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/2306 Química orgánicajournal article10.1002/anie.2025219221521-3773open access