2026-10-11T07:48:21Z https://api.figshare.com/v2/oai

oai:figshare.com:article/33791516 2026-09-15T12:11:15Z category_1 category_4 category_12 category_272 category_873 category_46 category_734 portal_63 item_type_3 month_year_09_2026

Structural Fluxionality of Surface Motifs in Positional Isomeric Au₁₄Cd₂ Clusters Enables Switchable O–O Bond Activation Pathways Yesen Tan (14094387) Yangping Wang (20824742) Qinzhen Li (4449457) Sha Yang (442752) Jinsong Chai (1547983) Baoyu Huang (388530) Ling Huang (51752) Manzhou Zhu (1269564) Biophysics Biochemistry Cell Biology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Immunology Biological Sciences not elsewhere classified reversible interconversion mediated radical pathway ). oxo pathway ), employed styrene oxidation distinct electronic distributions clusters enables switchable 3 %), whereas metal valence states high benzaldehyde selectivity bond activation pathways 2 </ sub 14 </ sub 13 </ sub positional isomeric au surface motif arrangements bond activation surface motifs tpp trapping substrate binding structural fluxionality results show physicochemical properties packing model nmr experiments independent modulation icosahedral kernel highly sensitive higher conversion epoxide selectivity effective strategy differ exclusively dft calculations decouple activity catalytic performance 9 %). 8 %) 1 %) The construction of positional isomers enables tunable control over the physicochemical properties of nanoclusters. However, up to now, the packing model of the core and motif has typically been one-to-one. Herein, we present positional isomeric nanoclusters, Au₁₄Cd₂-1 and Au₁₄Cd₂-2, which feature an identical Au₁₃ icosahedral kernel but differ exclusively in their surface motif arrangements, leading to distinct electronic distributions. This inherent structural fluxionality enables their reversible interconversion mediated by boranes. Capitalizing on distinct metal charge distributions of the isomers, we employed styrene oxidation (highly sensitive to metal valence states) as a mode to probe their catalytic performance. The results show that the electron-deficient Au₁₄Cd₂-1 achieves high conversion (93.1%) with epoxide selectivity (77.3%), whereas the electron-rich Au₁₄Cd₂-2 gives lower conversion (36.8%) but high benzaldehyde selectivity (88.9%). Mechanistic interrogation via TEMPO/TPP trapping of key intermediates revealed pathway bifurcation: Au₁₄Cd₂-1 follows heterolytic O–O cleavage (metal-oxo pathway), while Au₁₄Cd₂-2 undergoes homolytic cleavage (radical pathway). Furthermore, DFT calculations, together with XPS and NMR experiments, revealed stronger styrene binding affinity of Au₁₄Cd₂-1, consistent with its higher conversion. This work establishes positional isomerism as an effective strategy to decouple activity and selectivity through independent modulation of substrate binding and O–O bond activation. 2026-09-15T00:00:00Z Dataset Dataset 10.1021/acsnano.6c13482.s002 https://figshare.com/articles/dataset/Structural_Fluxionality_of_Surface_Motifs_in_Positional_Isomeric_Au_sub_14_sub_Cd_sub_2_sub_Clusters_Enables_Switchable_O_O_Bond_Activation_Pathways/33791516 CC BY-NC 4.0