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Here, we set to investigate the impact of ligand identity on the structural, bonding, and optical properties based on Au13Cl2 and Au13 cluster cores coordinated by bidentate ligands from phosphines to heavier pnictogens members, provided by arsine, stibine, and bismuthine, in isostructural prototypical templates. Our results reveal contrasting trends in Au\u2013Au core distances between Au13Cl2 and Au13 clusters upon ligand substitution, with Au\u2013L bond lengths increasing down the group, in addition to a systematic decrease in ligand\u2013core interaction energies driven by reduced electrostatic and orbital contributions, indicating weaker coordination and increased ligand lability for heavier ligands. Optical properties exhibit ligand-dependent UV\u2013vis absorption shifts and phosphorescent emissions, with heavier ligands causing notable red-shifts and altered excited-state geometries. These findings demonstrate the tunability of Au13 cluster properties through ligand modification, providing insights for designing superatomic clusters with tailored photophysical and chemical functionalities for catalysis and optoelectronic applications.<\/jats:p>","DOI":"10.1021\/acs.jpclett.6c02791","type":"journal-article","created":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T03:01:22Z","timestamp":1791255682000},"page":"11801-11808","source":"Crossref","is-referenced-by-count":0,"title":["Heavier Counterparts\nfor Phosphine-Protected Gold\nClusters. Electronic, Bonding, and Optical Properties of Au13Cl2(L5) and Au13(L6)\nSuperatoms"],"prefix":"10.1021","volume":"17","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5949-9449","authenticated-orcid":true,"given":"Alvaro","family":"Mun\u0303oz-Castro","sequence":"first","affiliation":[{"name":"Universidad San Sebastia\u0301n , , Bellavista 7 , ,","place":["Santiago, Chile, 8420524"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,10,5]]},"reference":[{"issue":"27","key":"2026101508213633700_cit1","doi-asserted-by":"publisher","first-page":"12052","DOI":"10.1021\/jacs.2c02218","article-title":"Visible-Light Copper Nanocluster Catalysis for the\nC\u2013N Coupling of Aryl Chlorides at Room Temperature","volume":"144","author":"Sagadevan","year":"2022","journal-title":"J. Am. Chem. 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