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The electronic properties of interfaces of both metal complexes were studied using photoelectron spectroscopy (XPS, UPS) and scanning tunneling microscopy (STM) in the monolayer and multilayer regimes. In the respective multilayers, the surface-decoupled complexes comprise paramagnetic cobalt centers, as indicated by the Co 2p core-level spectra. In the monolayers, both complexes are chemisorbed and engage in charge transfer at the interface. Consequently, the former singly occupied orbitals at the cobalt centers accept electron density from the Ag(111) surface. As a result, the cobalt centers of both complexes are reduced. Despite these similarities, there are substantial differences in the overall interaction strength: a much stronger interaction was observed in the case of the corrole complex, for which the interfacial charge transfer is not limited to the cobalt states, but also involves the ligand\u2019s [Formula: see text]-electron system. Density functional theory (DFT) calculations of the corresponding parent macrocycles reveal that, in comparison with the porphyrin, the corrole exhibits increased adsorption energy, a reduced adsorption height, and undergoes a stronger interfacial charge transfer. The increased stability of the corrole\/ metal interface is attributed to the corrole ligand\u2019s open-shell character with delocalized [Formula: see text]-electron spin density and the resulting stabilization by rearomatization-driven electron transfer. <\/jats:p>","DOI":"10.1142\/s1088424623500608","type":"journal-article","created":{"date-parts":[[2023,2,18]],"date-time":"2023-02-18T05:20:01Z","timestamp":1676697601000},"page":"670-681","source":"Crossref","is-referenced-by-count":0,"title":["Why can cobalt(III) corrole form more stable metal\/ organic interfaces than cobalt(II) porphyrin?"],"prefix":"10.1142","volume":"27","author":[{"given":"Jan","family":"Herritsch","sequence":"first","affiliation":[{"name":"Fachbereich Chemie, Philipps-Universit\u00e4t Marburg, Hans-Meerwein-Stra\u00dfe, 35032 Marburg, Germany"}]},{"given":"Malte","family":"Zugermeier","sequence":"additional","affiliation":[{"name":"Fachbereich Chemie, Philipps-Universit\u00e4t Marburg, Hans-Meerwein-Stra\u00dfe, 35032 Marburg, Germany"}]},{"given":"Martin","family":"Schmid","sequence":"additional","affiliation":[{"name":"Fachbereich Chemie, Philipps-Universit\u00e4t Marburg, Hans-Meerwein-Stra\u00dfe, 35032 Marburg, Germany"}]},{"given":"Min","family":"Chen","sequence":"additional","affiliation":[{"name":"Fachbereich Chemie, Philipps-Universit\u00e4t Marburg, Hans-Meerwein-Stra\u00dfe, 35032 Marburg, Germany"}]},{"given":"Jan-Niclas","family":"Luy","sequence":"additional","affiliation":[{"name":"Fachbereich Chemie, Philipps-Universit\u00e4t Marburg, Hans-Meerwein-Stra\u00dfe, 35032 Marburg, Germany"},{"name":"Wilhelm-Ostwald-Institut f\u00fcr Physikalische und Theoretische Chemie, Universit\u00e4t Leipzig, 04103 Leipzig, Germany"}]},{"given":"Peter","family":"Schweyen","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische und Analytische Chemie, Technische Universit\u00e4t Braunschweig, Hagenring 30, 38106 Braunschweig, Germany"}]},{"given":"Martin","family":"Br\u00f6ring","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische und Analytische Chemie, Technische Universit\u00e4t Braunschweig, Hagenring 30, 38106 Braunschweig, Germany"}]},{"given":"Ralf","family":"Tonner-Zech","sequence":"additional","affiliation":[{"name":"Fachbereich Chemie, Philipps-Universit\u00e4t Marburg, Hans-Meerwein-Stra\u00dfe, 35032 Marburg, Germany"},{"name":"Wilhelm-Ostwald-Institut f\u00fcr Physikalische und Theoretische Chemie, Universit\u00e4t Leipzig, 04103 Leipzig, Germany"}]},{"given":"J. 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