Control over the Self-Assembly Modes of PtII Complexes by Alkyl Chain Variation: From Slipped to Parallel π-Stacks
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- 作者：Dr. Naveen Kumar Allampally ; Dr. Marí ; a José ; Mayoral ; Dr. Sarayute Chansai ; Dr. Marí ; a Cristina Lagunas ; Prof. Christopher Hardacre ; Dr. Vladimir Stepanenko ; Prof. Rodrigo Q. Albuquerque and Prof. Dr. Gustavo Ferná ; ndez
- 刊名：Chemistry - A European Journal
- 出版年：2016
- 出版时间：June 1, 2016
- 年：2016
- 卷：22
- 期：23
- 页码：7810-7816
- 全文大小：2347K
- ISSN：1521-3765
文摘
We report the self-assembly of a new family of hydrophobic, bis(pyridyl) PtII complexes featuring an extended oligophenyleneethynylene-derived π-surface appended with six long (dodecyloxy (2)) or short (methoxy (3)) side groups. Complex 2, containing dodecyloxy chains, forms fibrous assemblies with a slipped arrangement of the monomer units (dPt⋅⋅⋅Pt≈14 Å) in both nonpolar solvents and the solid state. Dispersion-corrected PM6 calculations suggest that this organization is driven by cooperative π–π, C−H⋅⋅⋅Cl and π–Pt interactions, which is supported by EXAFS and 2D NMR spectroscopic analysis. In contrast, nearly parallel π-stacks (dPt⋅⋅⋅Pt≈4.4 Å) stabilized by multiple π–π and C−H⋅⋅⋅Cl contacts are obtained in the crystalline state for 3 lacking long side chains, as shown by X-ray analysis and PM6 calculations. Our results reveal not only the key role of alkyl chain length in controlling self-assembly modes but also show the relevance of Pt-bound chlorine ligands as new supramolecular synthons.