Control over the Self-Assembly Modes of PtII Complexes by Alkyl Chain Variation: From Slipped to Parallel π-Stacks

Naveen Kumar Allampally, Maria Jose Mayoral, Sarayute Chansai, Maria Cristina Lagunas, Christopher Hardacre, Vladimir Stepanenko, Rodrigo Q. Albuquerque, Gustavo Fern‚ndez

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

We report the self-assembly of a new family of hydrophobic,bis(pyridyl) PtII complexes featuring an extendedoligophenyleneethynylene-derived π-surface appended withsix 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 organizationis 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 contact sare obtained in the crystalline state for 3 lacking longside chains, as shown by X-ray analysis and PM6 calculations.Our results reveal not only the key role of alkyl chain lengthin controlling self-assembly modes but also show the relevanceof Pt-bound chlorine ligands as new supramolecular synthons.
Original languageEnglish
Pages (from-to)7810-7816
Number of pages7
JournalChemistry - A European Journal
Volume22
Issue number23
Early online date26 Apr 2016
DOIs
Publication statusPublished - 01 Jun 2016

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