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Control over the Self‐Assembly Modes of Pt II Complexes by Alkyl Chain Variation: From Slipped to Parallel π‐Stacks
Author(s) -
Allampally Naveen Kumar,
Mayoral María José,
Chansai Sarayute,
Lagunas María Cristina,
Hardacre Christopher,
Stepanenko Vladimir,
Albuquerque Rodrigo Q.,
Fernández Gustavo
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600176
Subject(s) - synthon , alkyl , crystallography , supramolecular chemistry , monomer , chemistry , self assembly , side chain , solid state , polymer chemistry , stereochemistry , materials science , crystal structure , organic chemistry , polymer
We report the self‐assembly of a new family of hydrophobic, bis(pyridyl) Pt II 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 (d Pt⋅⋅⋅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 (d Pt⋅⋅⋅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.