%0 Journal Article %A Zeng, Chenjie %A Liu, Chunyan %A Pei, Yong %A Jin, Rongchao %D 2013 %T Thiol Ligand-Induced Transformation of Au38(SC2H4Ph)24 to Au36(SPh‑t‑Bu)24 %U https://acs.figshare.com/articles/journal_contribution/Thiol_Ligand_Induced_Transformation_of_Au_sub_38_sub_SC_sub_2_sub_H_sub_4_sub_Ph_sub_24_sub_to_Au_sub_36_sub_SPh_i_t_i_Bu_sub_24_sub_/2393989 %R 10.1021/nn401971g.s001 %2 https://acs.figshare.com/ndownloader/files/4033681 %K theory simulations %K TBBT ligands %K nanocluster %K distortion %K activation energies %K spectroscopy analyses %K biicosahedral %K tetrahedral structure %K reaction kinetics %K absorption features %K disproportionation mechanism %K disproportionation steps %K ligand exchange %K disproportionation process %X We report a disproportionation mechanism identified in the transformation of rod-like biicosahedral Au38(SCH2CH2Ph)24 to tetrahedral Au36(TBBT)24 nanoclusters. Time-dependent mass spectrometry and optical spectroscopy analyses unambiguously map out the detailed size-conversion pathway. The ligand exchange of Au38(SCH2CH2Ph)24 with bulkier 4-tert-butylbenzenethiol (TBBT) until a certain extent starts to trigger structural distortion of the initial biicosahedral Au38(SCH2CH2Ph)24 structure, leading to the release of two Au atoms and eventually the Au36(TBBT)24 nanocluster with a tetrahedral structure, in which process the number of ligands is interestingly preserved. The other product of the disproportionation process, i.e., Au40(TBBT)m+2(SCH2CH2Ph)24–m, was concurrently observed as an intermediate, which was the result of addition of two Au atoms and two TBBT ligands to Au38(TBBT)m(SCH2CH2Ph)24–m. The reaction kinetics on the Au38(SCH2CH2Ph)24 to Au36(TBBT)24 conversion process was also performed, and the activation energies of the structural distortion and disproportionation steps were estimated to be 76 and 94 kJ/mol, respectively. The optical absorption features of Au36(TBBT)24 are interpreted on the basis of density functional theory simulations. %I ACS Publications