The templating effect of the tetrafluoroborate ion leads to assembly of four Co ions and six bridging ligands around this anion to give a tetrahedral complex with a bridging ligand along each edge and the anion trapped in the central cavity (shown below). Surprisingly under identical conditions but with Ni a simpler dinuclear complex forms.
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Intricate Low-Symmetry Ag Capsules Formed by Anion-Templated Self-Assembly of the Stereoisomers of an Unsymmetric Ligand.
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Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Metal-organic cages and capsules exhibit space-specific functions based on their discrete hollow structures. To acquire enzyme-like asymmetric or intricate structures, they have been modified by desymmetrization with two or more different ligands. There is a need to establish new strategies that can desymmetrize structures in a simple way using only one type of ligand, which is different from the mixed-ligand approach.
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National Dong Hwa University, Department of Chemistry, No. 1, Sec. 2, Da Hsueh Rd. Shoufeng, Hualien 97401, Taiwan, Republic of China.
Atomically precise clusters of group 11 metals (Cu, Ag, and Au) attract considerable attention owing to their remarkable structure and fascinating properties. One of the unique subclasses of these clusters is based on dichalcophosphate ligands of [(RO)PE] type (E = S or Se, and R = alkyl). These ligands successfully stabilise the most diverse Cu, Ag, and Au clusters and superatoms, spanning from simple ones to amazing assemblies featuring unusual structural and bonding patterns.
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Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an, 710069, P. R. China.
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View Article and Find Full Text PDFAnion-Driven Programmable Chiral Self-Sorting in Metal-Organic Cages and Structural Transformations between Heterochiral and Homochiral Cages.
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Organic and Medicinal Chemistry Division, CSIR Indian Institute of Chemical Biology, 4 Raja S C Mullick Road, 700031, Kolkata, India.
When a racemic mixture of chiral building blocks self-assembles to form discrete molecular or supramolecular cages, the system can adopt either social or narcissistic chiral self-sorting. However, control over such chiral self-sorting is hard to achieve with a desired choice of outcome. Herein, we report anion templated high-fidelity chiral self-sorting during the coordination-driven self-assembly of [Pd L ] metal-organic cages, with a racemic mixture of an axially chiral ligand.
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October 2022
A State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology (HUST), Wuhan 430074, China.
Under the guidance of anion templates VO and SO, the novelty of cluster assembly can be increased by using different carboxylate ligands. Herein, the synthesis, crystal structure and electrochemical properties of three anion-templated silver thiolated clusters are reported, namely VO@Ag(PrS)(CFCO)(DMF) (1), VO@Ag(PrS)(CFCO)(PhCO)(DMF) (2), and [SO@Ag(PrS)(PTA)(HPTA)] (3, HPTA = phthalic acid). Single-crystal X-ray diffraction analysis showed that 1 and 2 are discrete clusters VO@Ag.
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