Ligand‐Directed Template Assembly for the Construction of Gigantic Molybdenum Blue Wheels

• Published in: Angewandte Chemie International Edition Vol. 58; no. 32; pp. 10867 - 10872
• Main Authors: Xuan, Weimin, Pow, Robert, Zheng, Qi, Watfa, Nancy, Long, De‐Liang, Cronin, Leroy
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 05-08-2019; John Wiley and Sons Inc
• Edition: International ed. in English
• Subjects: anion templation; Assembly; Communication; Communications; Construction; Functional materials; gigantic cluster; host–guest chemistry; Ligands; Molybdenum; molybdenum blue; Ornithine; polyoxometalates; anion templation; gigantic cluster; molybdenum blue; host-guest chemistry; polyoxometalates
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201901818

Template‐mediated synthesis is a powerful approach to build a variety of functional materials and complex supramolecular systems. However, the systematic study of how templates structurally evolve from basic building blocks, and then affect the templated self‐assembly, is critical to understanding and utilizing the underlying mechanism, to work towards designed assembly. Here we describe the templated self‐assembly of a series of gigantic Mo Blue (MB) clusters 1–4 using l‐ornithine as a structure‐directing ligand. We show that by using l‐ornithine as a structure director, we can form new template⊂host assemblies. Based on the structural relationship between encapsulated templates of {Mo8} (1), {Mo17} (2) and {Mo36} (4), a pathway of the structural evolution of templates is proposed. This provides insight into how gigantic Mo Blue cluster rings form and could lead to full control over the designed assembly of gigantic Mo‐blue rings.
Gigantic Mo Blue clusters with ligand directed template⊂host architectures are constructed via anion‐templated self‐assembly with l‐ornithine as structure‐directing agent. Based on the structural relationship between encapsulated templates of {Mo8}, {Mo17} and {Mo36}, a pathway of the structural evolution of templates can be proposed.