Ligand Aspect Ratio as a Decisive Factor for the Self-Assembly of Coordination Cages
| Autor: | Yan Z. Voloshin, Alba Finelli, Genrikh E. Zelinskii, Jonathan R. Nitschke, Anna V. Vologzhanina, Kay Severin, Tanya K. Ronson, Konstantin O. Zhurov, Giacomo Cecot, Philip Pattison, Matthew D. Wise, Suzanne M. Jansze, Ana M. Castilla, Rosario Scopelliti, Euro Solari |
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| Rok vydání: | 2016 |
| Předmět: |
Clathrochelate
010405 organic chemistry Ligand Stereochemistry Chemistry General Chemistry 010402 general chemistry 01 natural sciences Biochemistry Aspect ratio (image) Catalysis 0104 chemical sciences Condensed Matter::Soft Condensed Matter Crystallography Colloid and Surface Chemistry Large aspect ratio Octahedron Physics::Atomic and Molecular Clusters Tetrahedron Cage |
| Zdroj: | Journal of the American Chemical Society. 138(6) |
| ISSN: | 1520-5126 |
| Popis: | It is possible to control the geometry and the composition of metallasupramolecular assemblies via the aspect ratio of their ligands. This point is demonstrated for a series of iron- and palladium-based coordination cages. Functionalized clathrochelate complexes with variable aspect ratios were used as rod-like metalloligands. A cubic Fe(II)8L12 cage was obtained from a metalloligand with an intermediate aspect ratio. By increasing the length or by decreasing the width of the ligand, the self-assembly process resulted in the clean formation of tetrahedral Fe(II)4L6 cages instead of cubic cages. In a related fashion, it was possible to control the geometry of Pd(II)-based coordination cages. A metalloligand with a large aspect ratio gave an entropically favored tetrahedral Pd(II)4L8 assembly, whereas an octahedral Pd(II)6L12 cage was formed with a ligand of the same length but with an increased width. The aspect ratio can also be used to control the composition of dynamic mixtures of Pd(II) cages. Out of two metalloligands with only marginally different aspect ratios, one gave rise to a self-sorted collection of Pd(II)4L8 and Pd(II)6L12 cages, whereas the other did not. |
| Databáze: | OpenAIRE |
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