Synthesis, Structure, and Properties of Supramolecular Charge-Transfer Complexes between Bis(18-crown-6)stilbene and Ammonioalkyl Derivatives of 4,4'-Bipyridine and 2,7-Diazapyrene

4,4'-Bipyridine and 2,7-diazapyrene derivatives (A) having two ammonioalkyl N-substituents were synthesized. The complex formation of these compounds with bis(18-crown-6)stilbene (D) was studied by spectrophotometry, cyclic voltammetry, (1)H NMR spectroscopy, and X-ray diffraction analysis. In MeCN, pi-donor D and pi-acceptors A form supramolecular 1:1 (D . A) and 2:1 (D . A . D) charge-transfer complexes. The D . A complexes have a pseudocyclic structure as a result of ditopic binding of the ammonium groups to the crown-ether fragments. The better the geometric matching between the components, the higher the stability of the D . A complexes (log K up to 9.39). A key driving force of the D. A . D complex formation is the excessive steric strain in the precursor D . A complexes. The pseudocyclic D . A complexes involving the ammoniopropyl derivative of 4,4'-bipyridine were obtained as single crystals. Crystallization of the related ammonioethyl derivative was accompanied by transition of the D . A complexes to a structure of the (D . A)(m) coordination polymer type.