Gold(I) thiolate compounds (i.e. AuLSR) are important precursors for the synthesis of atom- ically precise Aun(SR)m nanoclusters. However, the nature of the AuI-SR precursor remains elusive. Here, we report that...Gold(I) thiolate compounds (i.e. AuLSR) are important precursors for the synthesis of atom- ically precise Aun(SR)m nanoclusters. However, the nature of the AuI-SR precursor remains elusive. Here, we report that the Aul0(TBBT)10 complex is a universal precursor for the synthesis of Aun(TBBT)m nanoclusters (where TBBT 4-tertbutylbenzenethiol/thiolate). Interestingly, the Aul0(TBBT)10 complex is also found to be re-generated through extended etching of the Aun(SR)m nanoclusters with excess of TBBT thiol and O2. The formation of well-defined Aul0(TBBT)10 complex, instead of polymeric AuKSR, is attributed to the bulkiness of the TBBT thiol. Through 1D and 2D NMR charcteriztions, the structure of Aul0(TBBT)10 is correlated with the previously reported X-ray structure, which contains two inter-penetrated Aus(TBBT)5 rings. The photophysical property of Au10(TBBT)10 complex is further probed by femtosecond transient absorption spectroscopy. The acces- sibility of the precise Au10(TBBT)10 precursor improves the efficiency of the synthesis of the Aun(TBBT)m nanoclusters and is expected to further facilitate excellent control and understanding of the reaction mechanisms of nanocluster synthesis.展开更多
基金supported by the U.S.National Science Foundation(DMR-1808675)
文摘Gold(I) thiolate compounds (i.e. AuLSR) are important precursors for the synthesis of atom- ically precise Aun(SR)m nanoclusters. However, the nature of the AuI-SR precursor remains elusive. Here, we report that the Aul0(TBBT)10 complex is a universal precursor for the synthesis of Aun(TBBT)m nanoclusters (where TBBT 4-tertbutylbenzenethiol/thiolate). Interestingly, the Aul0(TBBT)10 complex is also found to be re-generated through extended etching of the Aun(SR)m nanoclusters with excess of TBBT thiol and O2. The formation of well-defined Aul0(TBBT)10 complex, instead of polymeric AuKSR, is attributed to the bulkiness of the TBBT thiol. Through 1D and 2D NMR charcteriztions, the structure of Aul0(TBBT)10 is correlated with the previously reported X-ray structure, which contains two inter-penetrated Aus(TBBT)5 rings. The photophysical property of Au10(TBBT)10 complex is further probed by femtosecond transient absorption spectroscopy. The acces- sibility of the precise Au10(TBBT)10 precursor improves the efficiency of the synthesis of the Aun(TBBT)m nanoclusters and is expected to further facilitate excellent control and understanding of the reaction mechanisms of nanocluster synthesis.