Anion-Orchestrated Formation in the Crystalline State of [2]Pseudorotaxane Arrays

Abstract

In contrast with dibenzo[24]crown-8 (DB24C8), when tetrabenzo[24]crown-8 (TB24C8) is mixed with dibenzylammonium hexafluorophosphate (DBA·PF6) in noncompetitive solvents, the thermodynamically driven noncovalent synthesis of the threaded 1:1 complexa [2]pseudorotaxanedoes not occur. However, on crystallization from solutionin a process which is presumably kinetically controlledTB24C8 molecules and DBA+ cations form an array of [2]pseudorotaxanes stabilized by a plethora of [C−H···F] hydrogen bonds to highly ordered, interstitially located PF6- anions.