Control over the Self‐Assembly Modes of PtII Complexes by Alkyl Chain Variation: From Slipped to Parallel π‐Stacks |
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| Authors: | Dr. Naveen Kumar Allampally Dr. María José Mayoral Dr. Sarayute Chansai Dr. María Cristina Lagunas Prof. Christopher Hardacre Dr. Vladimir Stepanenko Prof. Rodrigo Q. Albuquerque Prof. Dr. Gustavo Fernández |
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| Affiliation: | 1. Institut für Organische Chemie and Center for Nanosystems Chemistry, Universit?t Würzburg, Würzburg, Germany;2. Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Madrid, Spain;3. School of Chemistry and Chemical Engineering, Queen's Universtity Belfast, Belfast, United Kingdom;4. S?o Carlos Institute of Chemistry, University of S?o Paulo, A, S?o Carlos-SP, Brazil;5. Organisch-Chemisches Institut, Westf?lische Wilhelms-Universit?t Münster, Münster, Germany |
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| Abstract: | 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. |
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| Keywords: | cooperative effects noncovalent interactions pi-interactions self-assembly solid-state structures |
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