State Key Lab of Physical Chemistry of Solid Surfaces Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen, Fujian, People' s Republic of China.
J Am Chem Soc. 2013 Oct 30;135(43):16184-91. doi: 10.1021/ja4075419. Epub 2013 Oct 17.
Cluster-based functional materials are appealing, because clusters are well-defined building units that can be rationally incorporated for the tuning of structures and properties. Postclustering modification (PCM) allows for tailoring properties through the structural modification of a cluster with preorganized funtional groups. By introducing aldehydes into a robust gold-silver cluster via a protection-deprotection process, we manage to synthesize a new cluster bearing six reactive sites, which are available for PCM through dynamic covalent imine bonds formation with chiral monoamines. Chirality is transferred from the amine to the gold-silver cluster. The homochirality of the resulted cluster has been confirmed by X-ray structural determination and CD spetroscopy. Intense CD signals make it practical for chiral recognition and ee value determination of chiral monoamines. The strategy of prefunctionalizing of cluster and the concept of PCM open a broader prospect for cluster design and applications.
基于团簇的功能材料具有吸引力，因为团簇是定义明确的构建单元，可以通过合理地组合来调整结构和性质。后团簇修饰（PCM）允许通过用预组织的功能基团对团簇进行结构修饰来定制性质。通过在一个坚固的金银团簇中引入醛，通过保护-脱保护过程，我们成功地合成了一个带有六个反应性位点的新团簇，这些位点可以通过与手性单胺形成动态共价亚胺键进行 PCM。手性从胺转移到金银团簇。通过 X 射线结构测定和 CD 光谱证实了所得团簇的同手性。强烈的 CD 信号使其可用于手性单胺的手性识别和 ee 值测定。预官能团化团簇的策略和 PCM 的概念为团簇设计和应用开辟了更广阔的前景。
