title: Amphiphilic perylene-calix[4]arene hybrids: synthesis and tunable self-assembly.
abstract: The first highly water-soluble perylene-calix[4]arene hybrid with the calixarene scaffold acting as a structure-determining central platform is presented. In this tetrahedrally shaped amphiphilic architecture the hydrophilic and hydrophobic subunits are oriented at the opposite side of the calixarene platform. The hydrophobic part contains the two perylene diimide moieties, which enable strong π-π interactions in self-assembly processes. Two hydrophilic Newkome-type dendrons provide sufficient water solubility at slightly basic conditions. The tetrahedrally shaped amphiphile displays an unprecedented aggregation behavior down to concentrations as low as 10(-7) mol L(-1). The intriguing self-assembly process of the compound in water as well as under changed polarity conditions, achieved by addition of THF, could be monitored by the complemented use of cryogenic transmission electron microscopy (cryo-TEM), UV-vis spectroscopy, and fluorescence spectroscopy. Molecular-dynamics and molecular modeling simulations helped in understanding the interplay of supramolecular and optical behavior.
authors.affiliation: Department of Chemistry and Pharmacy, Interdisciplinary Center of Molecular Materials (ICMM), Friedrich-Alexander-University of Erlangen-Nürnberg , Henkestrasse 42, 91054 Erlangen, Germany.
authors.forename: Fabian
authors.initials: F
authors.lastname: Rodler
authors.forename: Boris
authors.initials: B
authors.lastname: Schade
authors.forename: Christof M
authors.initials: CM
authors.lastname: Jäger
authors.forename: Susanne
authors.initials: S
authors.lastname: Backes
authors.forename: Frank
authors.initials: F
authors.lastname: Hampel
authors.forename: Christoph
authors.initials: C
authors.lastname: Böttcher
authors.forename: Timothy
authors.initials: T
authors.lastname: Clark
authors.forename: Andreas
authors.initials: A
authors.lastname: Hirsch
mesh_terms: D047250:Calixarenes / Q000138:chemical synthesis / Q000737:chemistry*; D060326:Chemistry Techniques, Synthetic; D020285:Cryoelectron Microscopy / Q000379:methods; D057927:Hydrophobic and Hydrophilic Interactions; D046529:Microscopy, Electron, Transmission / Q000379:methods; D008958:Models, Molecular; D056004:Molecular Dynamics Simulation; D010569:Perylene / Q000138:chemical synthesis / Q000737:chemistry*; D012995:Solubility; D013050:Spectrometry, Fluorescence; D013056:Spectrophotometry, Ultraviolet; D014867:Water / Q000737:chemistry
chemical_list: D014867:Water; D047250:Calixarenes; D010569:Perylene