RESUMO
The physicochemical properties of highly stable supramolecular donor-acceptor (D-A) complexes of a bis(18-crown-6)azobenzene (weak π-donor) with a series of bis(ammonioalkyl) derivatives of viologen-like molecules (π-acceptors) in acetonitrile were studied using cyclic voltammetry, UV-vis absorption spectroscopy, 1H NMR spectroscopy, and density functional theory (DFT) calculations. The crystalline structures of the bis(crown)azobenzene and its complex with a bis(ammoniopropyl) derivative of 2,7-diazapyrene were determined by X-ray diffraction analysis. In solution, all of the supramolecular D-A complexes studied have a pseudocyclic structure owing to ditopic coordination of the ammonium groups of the acceptor to the crown ether moieties of the donor. These complexes show somewhat lower stability as compared with the previously studied complexes of the related derivative of stilbene (strong π-donor), which is explained by the relatively weak intermolecular charge-transfer (CT) interactions. Time-dependent DFT calculations predict that the low-energy CT transition in the D-A complex of the bis(crown)azobenzene with a bis(ammoniopropyl) derivative of 4,4'-bipyridine lies between the local ππ* and nπ* transitions of the azobenzene. The absorption band associated with the CT transition is indiscernible in the spectrum since it is overlapped with broad and more intense ππ* and nπ* bands. It was found that the E â Z photoisomerization quantum yield of the bis(crown)azobenzene decreases by almost an order of magnitude upon the complexation with the 4,4'-bipyridine derivative. This effect was tentatively attributed to the intermolecular electron transfer that occurs in the 1ππ* excited state of the azobenzene and competes with the 1ππ* â 1 nπ* internal conversion.
RESUMO
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, π-donor D and π-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.
