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oai:figshare.com:article/34039569 2026-10-01T05:39:48Z category_37 portal_316 item_type_3 month_year_10_2026

Table 1_Aurophilicity as a structure-directing principle in hyperchlorinated AunCln+5- (2 ≤ n ≤ 7) clusters.docx Yuqing Chen (231681) Shiyin Xu (12249967) Shuo Wang (143908) Shuqi Li (9017438) Filip Veljković (18133129) Suzana Veličković (18133132) Xianglei Kong (796083) Organic Chemistry aurophilicity binding energy gold chloride cluster mass spectrometry structure <p>This study addresses the gap concerning the structural landscape of experimentally observed high-chloride Au_nCl_n+5^- cluster anions, whose stable geometries, aurophilic interaction patterns, thermodynamic stability, and growth pathways remain largely unexplored compared to well-characterized low- and medium-chloride analogues. To resolve this, we systematically investigate Au_nCl_n+5^- (n = 2–7) using laser desorption/ionization mass spectrometry (LDI-MS) and density functional theory at the TPSSh/aug-cc-pVTZ/ECP60MDF level. The results show that elevated laser intensity preferentially stabilizes these chlorine-rich clusters. Except for the smallest cluster (Au₂Cl₇⁻), the global minima adopt nearly planar zigzag geometries, where terminal gold atoms are in a tetracoordinate Au(III) state and internal gold atoms are in an Au(I) state. Bond-length analysis reveals that only non-terminal Au–Au distances are significantly shorter than the van der Waals sum, indicating aurophilic attraction, while terminal distances show no such interaction. Aurophilicity emerges at Au₄Cl₉⁻ and rapidly stabilizes for larger clusters. Natural bond orbital (NBO) and electron localization function (ELF) analyses attribute this interaction to 6s/5d orbital delocalization between adjacent Au(I) centers, with no contribution from Au(III)–Au(I) pairs. Comparison with lower-chloride series (Au_nCl_n+1⁻ and Au_nCl_n+3⁻) indicates that the core thermodynamic trend remains unchanged, although higher laser fluence favors chlorine-rich species via thermodynamically favored addition of two Cl atoms. This study highlights the structure-directing role of aurophilicity in hyperchlorinated gold clusters and provides a comprehensive understanding of their size-dependent structural evolution.</p> 2026-10-01T05:39:48Z Dataset Dataset 10.3389/fchem.2026.1986508.s001 https://figshare.com/articles/dataset/Table_1_Aurophilicity_as_a_structure-directing_principle_in_hyperchlorinated_AunCln_5-_2_n_7_clusters_docx/34039569 CC BY 4.0