A highly soluble pyrene-fused undecacene is realized by end-capping the rectilinear aromatic p-plane with triptycenylene units. Besides the good solubility, the compound shows a high tendency to crystallize. Two polymorphs from dichlorobenzene and chloroform are described. In the polymorph from chloroform, half of the molecules are strongly bent out of the p-plane by 26.4°. [ABSTRACT FROM AUTHOR]
Hafezi, Nema, Holcroft, James M., Hartlieb, Karel J., Dale, Edward J., Vermeulen, Nicolaas A., Stern, Charlotte L., Sarjeant, Amy A., and Stoddart, J. Fraser
We report the template-directed synthesis of BlueCage6+, a macrobicyclic cyclophane composed of six pyridinium rings fused with two central triazines and bridged by three paraxylylene units. These moieties endow the cage with a remarkably electron-poor cavity, which makes it a powerful receptor for polycyclic aromatic hydrocarbons (PAHs). Upon forming a 1:1 complex with pyrene in acetonitrile, however, BlueCage⋅6 PF6 exhibits a lower association constant Ka than its progenitor ExCage⋅6 PF6. A close inspection reveals that the six PF6− counterions of BlueCage6+ occupy the cavity in a fleeting manner as a consequence of anion-π interactions and, as a result, compete with the PAH guests. This conclusion is supported by a one order of magnitude increase in the Ka value for pyrene in BlueCage6+ when the PF6− counterions are replaced by much bulkier anions. The presence of anion-π interactions is supported by X-ray crystallography, and confirms the presence of a PF6− counterion inside its cavity. [ABSTRACT FROM AUTHOR]