Controlling the Structure, Properties and Surface Reactivity of Clickable Azide-Functionalized Au25(SR)18 Nanocluster Platforms Through Regioisomeric Ligand Modifications.
Controlling the Structure, Properties and Surface Reactivity of Clickable Azide-Functionalized Au25(SR)18 Nanocluster Platforms Through Regioisomeric Ligand Modifications.
复制标题
通过区域异构配体修饰控制可点击叠氮化物功能化 Au25(SR)18 纳米团簇平台的结构、性质和表面反应性。
DOI：
10.1002/anie.202205194
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发表时间：
2022
影响因子：
--
通讯作者：
M. Workentin
中科院分区：
文献类型：
--
作者：
Pravneen Gunawardene;Julia Martín;J. Wong;Z. Ding;J. Corrigan;M. Workentin
为了通过组装后表面修饰来微调硫醇保护的金纳米团簇的结构-性质相关性，我们报道了阴离子叠氮功能化的[AU25(SCH2CH2-C6H4-N3)18]1-平台的<；italic>；o<；/italic>；、<；italic>；m<；/italic>；和<；italic>；p<；/italic>；区域异构体形式的合成。它们可以与互补的应变炔进行簇面应变促进的炔叠氮环加成(<；italic>；cs<；/italic>；-spaac)化学。尽管它们的光学性质相似，但电化学性质似乎与叠氮基团的位置有关。在不改变母体纳米簇合物结构的情况下进行<；italic>；CS<；/italic&SPAAC化学的能力随着表面配体的异构体形式的改变而不同，其中[Au25(SCH2CH2-<；italic>；p<；/italic>；-C6H4-N3)18]1-异构体具有最高的反应速率，而[Au25(SCH2CH2-<；italic>；o<；/italic>；-C6H4-N3)18]1-异构体不稳定。/italic>；-空格。单晶X射线衍射提供了三个区域异构体簇合物[Au25(SCH2CH2-<；italic>；o<；/italic>；/<；italic>；m<；/italic>；/<；italic>；p<；/italic>；-C6H4-N3]0，的中性形式的分子结构，它说明了随着叠氮部分的位置改变而中心核的相关结构特征。
<p class="Abstract" style="margin: 0cm 0cm 30pt; text-align: justify; line-height: 11.25pt; font-size: 8pt; font-family: Arial, sans-serif; color: rgb(0, 0, 0);"><span lang="EN-GB">To fine-tune structure-property correlations of thiolate-protected gold nanoclusters through post-assembly surface modifications, we report the synthesis of the <italic>o</italic>, <italic>m</italic>, and <italic>p</italic> regioisomeric forms of the anionic azide-functionalized [Au25(SCH2CH2-C6H4-N3)18]1- platform. They can undergo cluster-surface strain-promoted alkyne-azide cycloaddition (<italic>CS</italic>-SPAAC) chemistry with complementary strained-alkynes. Although their optical properties are similar, the electrochemical properties appear to correlate with the position of the azido group. The ability to conduct <italic>CS</italic>-SPAAC chemistry without altering the parent nanocluster structure is different as the isomeric form of the surface ligand is changed, with the [Au25(SCH2CH2-<italic>p</italic>-C6H4-N3)18]1- isomer having the highest reaction rates, while the [Au25(SCH2CH2-<italic>o</italic>-C6H4-N3)18]1- isomer is not stable following <italic>CS</italic>-SPAAC. Single-crystal X-ray diffraction provide the molecular structure of the neutral forms of the three regioisomeric clusters, [Au25(SCH2CH2-<italic>o</italic>/<italic>m</italic>/<italic>p</italic>-C6H4-N3]0, which illustrates correlated structural features of the central core as the position of the azido moiety is changed.<o:p></o:p></span></p>.