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Control over the Self-Assembly Modes of Pt<sup>II</sup> Complexes by Alkyl Chain Variation: From Slipped to Parallel π-Stacks

Allampally, NK and Mayoral, MJ and Chansai, S and Lagunas, MC and Hardacre, C and Stepanenko, V and Albuquerque, RQ and Fernández, G (2016) Control over the Self-Assembly Modes of Pt<sup>II</sup> Complexes by Alkyl Chain Variation: From Slipped to Parallel π-Stacks. Chemistry - A European Journal, 22 (23). pp. 7810-7816. ISSN 0947-6539

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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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Item Type: Article
Uncontrolled Keywords: 03 Chemical Sciences
Subjects: Q Science > QD Chemistry
Divisions: Pharmacy & Biomolecular Sciences
Publisher: Wiley
Date Deposited: 21 Sep 2016 08:30
Last Modified: 07 Sep 2017 13:05
DOI or Identification number: 10.1002/chem.201600176
URI: http://researchonline.ljmu.ac.uk/id/eprint/4162

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