Counterion‐Assisted Shaping of Nanocluster Supracrystals1. Issue 1 (5th November 2014)

• Record Type: Journal Article
• Authors: Yao, Qiaofeng; Yu, Yue; Yuan, Xun; Yu, Yong; Zhao, Dan; Xie, Jianping; Lee, Jim Yang
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 1(2015)
• Page Start: 184
• Page End: 189
• Publication Date: 2014-11-05
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201408675
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Ag₄₄(<italic>p</italic>‐MBA)₃₀⁴⁻ (<italic>p</italic>‐MBA=<italic>para</italic>‐mercaptobenzoic acid) nanocluster (NC) supracrystals (SCs) with customizable shapes can be obtained by simply altering the type and concentration of the counterions of the <italic>p</italic>‐MBA ligands in the dimethylsulfoxide (DMSO)/water crystallization system. Changing the counterion of the <italic>p</italic>‐MBA ligand from H⁺ to Cs⁺ eliminates the directional hydrogen bonds in the SCs, resulting in the packing of deprotonated Ag₄₄(<italic>p</italic>‐MBA)₃₀⁴⁻ NCs into octahedral SCs, which is in stark contrast to the rhombohedral SCs that were formed by the packing of protonated Ag₄₄(<italic>p</italic>‐MBA)₃₀⁴⁻ NCs in previous studies. Furthermore, the double layer of deprotonated Ag₄₄(<italic>p</italic>‐MBA)₃₀⁴⁻ NCs is sensitive to charge screening induced by increasing the Cs⁺ concentration, thereby providing a means to regulate the precipitation kinetics of the Ag₄₄(<italic>p</italic>‐MBA)₃₀⁴⁻ NCs for SC shape engineering. Slow precipitation kinetics was found to favor over‐growth at the corners and edges of the octahedral SC nuclei, shaping the SCs into concave octahedra.</p> </abstract>