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Here, we investigate the formation, structure, thermal stability, and chemical robustness of phenyl- and triptycene-based SAMs deposited on naturally oxidized aluminum (\u223c1 nm AlOx). The effects of anchoring group chemistry (carboxylic vs phosphonic acid) and bonding mode (monopodal vs tripodal) are systematically compared. X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy confirm the formation of densely packed, upright-oriented \u223c1 nm thick monolayers irrespective of molecular architecture. Thermally programmed XPS reveals that phosphonic acid anchoring significantly increases desorption energies relative to carboxylic acid analogues, while tripodal binding provides an additional stability enhancement, yielding a high desorption energy of \u223c1.9 eV. Exchange experiments demonstrate exceptional chemical robustness of tripodal phosphonic acid monolayers. These findings establish phosphonic acid anchoring combined with tripodal binding as an effective strategy for engineering ultrathin, highly stable aromatic interfaces on technologically relevant oxide surfaces.<\/jats:p>","DOI":"10.1021\/acs.jpclett.6c02547","type":"journal-article","created":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T15:03:56Z","timestamp":1789571036000},"page":"11261-11270","source":"Crossref","is-referenced-by-count":0,"title":["Ultrathin and\nStable Aromatic Monolayers on Naturally\nOxidized Aluminum: The Role of Type and Number of Anchoring Groups"],"prefix":"10.1021","volume":"17","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5682-3936","authenticated-orcid":true,"given":"Anna","family":"Rojek","sequence":"first","affiliation":[{"name":"Smoluchowski Institute of Physics , , \u0141ojasiewicza 11 , ,","place":["Krako\u0301w, Poland, 30-348"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marta","family":"Szatny","sequence":"additional","affiliation":[{"name":"Smoluchowski Institute of Physics , , \u0141ojasiewicza 11 , ,","place":["Krako\u0301w, Poland, 30-348"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8597-2006","authenticated-orcid":true,"given":"Daria M.","family":"Cegie\u0142ka","sequence":"additional","affiliation":[{"name":"Smoluchowski Institute of Physics , , \u0141ojasiewicza 11 , ,","place":["Krako\u0301w, Poland, 30-348"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1902-100X","authenticated-orcid":true,"given":"\u0141ukasz","family":"Bodek","sequence":"additional","affiliation":[{"name":"Smoluchowski Institute of Physics , , \u0141ojasiewicza 11 , ,","place":["Krako\u0301w, Poland, 30-348"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8437-1965","authenticated-orcid":true,"given":"Yoshiaki","family":"Shoji","sequence":"additional","affiliation":[{"name":"Institute of Science Tokyo , , ,","place":["Yokohama, Japan, 226-8501"]},{"name":"Institute of Science Tokyo , , ,","place":["Yokohama, Japan, 226-8501"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Takanori","family":"Fukushima","sequence":"additional","affiliation":[{"name":"Institute of Science Tokyo , , ,","place":["Yokohama, Japan, 226-8501"]},{"name":"Institute of Science Tokyo , , ,","place":["Yokohama, Japan, 226-8501"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3708-7571","authenticated-orcid":true,"given":"Michael","family":"Zharnikov","sequence":"additional","affiliation":[{"name":"Heidelberg University , , Im Neuenheimer Feld 253 , ,","place":["Heidelberg, Germany, D-69120"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6131-4618","authenticated-orcid":true,"given":"Piotr","family":"Cyganik","sequence":"additional","affiliation":[{"name":"Smoluchowski Institute of Physics , , \u0141ojasiewicza 11 , ,","place":["Krako\u0301w, Poland, 30-348"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,16]]},"reference":[{"issue":"27","key":"2026100109090618400_cit1","doi-asserted-by":"publisher","DOI":"10.1002\/adfm.202418863","article-title":"Concurrent Interface Passivation\nand Contact Work Function Tuning in Organic Self-Aligned Gate Transistors\nand Complementary Circuits Using Phosphonic Acid Self-Assembled Monolayers","volume":"35","author":"Luo","year":"2025","journal-title":"Adv. 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Electron Spectrosc.\nRelated Phenomena"},{"issue":"1","key":"2026100109090618400_cit38","doi-asserted-by":"publisher","DOI":"10.1002\/admi.202500954","article-title":"Modification of Self-Assembled Monolayers by Electron\nIrradiation as a Tool for Surface Engineering, Lithography, and Nanofabrication","volume":"13","author":"Terfort","year":"2026","journal-title":"Adv. Mater. Interfaces"},{"key":"2026100109090618400_cit39","doi-asserted-by":"publisher","first-page":"203","DOI":"10.1016\/0042-207X(62)90978-8","article-title":"Thermal\nDesorption of Gases","volume":"12","author":"Redhead","year":"1962","journal-title":"Vacuum"},{"issue":"50","key":"2026100109090618400_cit40","doi-asserted-by":"publisher","first-page":"28031","DOI":"10.1021\/acs.jpcc.7b09685","article-title":"Relative Thermal Stability\nof Thiolate-\nand Selenolate-Bonded Aromatic Monolayers on the Au(111) Substrate","volume":"121","author":"Ossowski","year":"2017","journal-title":"J. Phys. Chem. 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