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ID: 17084.0, MPI für biophysikalische Chemie / Spektroskopie und photochemische Kinetik (Prof. Jürgen Troe)
Supramolecular assemblies of photochromic benzodithia-18-crown- 6 ethers in crystals, solutions, and monolayers
Authors:Fedorova, O. A.; Fedorov, Y. V.; Vedernikov, A. I.; Yescheoulova, O. V.; Gromov, S. P.; Alfimov, M. V.; Kuzmina, L. G.; Churakov, A. V.; Howard, J. A. K.; Zaitsev, S. Y.; Sergeeva, T. I.; Moebius, D.
Date of Publication (YYYY-MM-DD):2002
Title of Journal:New Journal of Chemistry
Issue / Number:5
Start Page:543
End Page:553
Review Status:Peer-review
Audience:Not Specified
Abstract / Description:We studied the assembly of dithiacrown ether styryl dye (CSD) molecules in crystals, solutions, and films in the presence of metal cations. X-Ray diffraction data allowed us to conclude that the anion affects the supramolecular architecture of CSDs in the crystal, specifically, the type of stacking of the dye molecules. In solution, in the presence of Pb2+, CSD molecules with the betaine structure spontaneously form dimeric complexes consisting of two dye molecules and two metal cations, with a fixed mutual arrangement of the double bonds. The dimer complex is stable due to coordination between the anion substituent of one molecule and the metal cation located in the crown ether cavity of the other molecule. Irradiation of the dimer complexes leads to regio- and stereoselective [2+2]- cycloaddition, giving only one cyclobutane derivative of the eleven theoretically possible products. The other photoreaction studied for CSDs is reversible Z-E isomerization. Due to its specific structure, the betaine-type CSD is able to form the anion-capped Z-isomer. Intramolecular coordination in the 'anion-capped' isomer enhances its stability and causes a sharp deceleration of its dark Z-E isomerization. The amphiphilic CSD forms relatively stable monolayers on distilled water and various aqueous salt subphases. The results obtained indicate that it is possible to distinguish between two types of the dye monolayer structures based on the presence of alkali or heavy metal cations in the aqueous subphase.
Comment of the Author/Creator:Date: 2002
External Publication Status:published
Document Type:Article
Communicated by:N. N.
Affiliations:MPI für biophysikalische Chemie/Abt. Jürgen Troe / 010
External Affiliations:Russian Acad Sci, Photochem Ctr, 7A Novatorov St, Moscow; 117421, Russia; Russian Acad Sci, Photochem Ctr, Moscow 117421, Russia; Russian Acad Sci, Inst Gen & Inorgan Chem, Moscow 117909, Russia; Univ Durham, Dept Chem, Durham DH1 3LE, England; Russian Acad Sci, Inst Bioorgan Chem, Moscow 117871, Russia
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