Stilbene Bis-Crown Ethers: Synthesis, Complexation and Photoisomerization.

Lindsten, Göran; Wennerström, Olof; Thulin, Bengt; Procházka, Michal; Tang, Pui-Fun Louisa; Ljungqvist, Anders

doi:10.3891/acta.chem.scand.40b-0545

Cited by 31 publications

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“…18 [(E) 2 (2,3,5,6,8,9,11,12,14,15 Decahydro 1,4,7,10,13,16 benzohexaoxacyclooctadecin 18 yl) 1 ethenyl] 2,3,5,6,8,9,11, 12,14,15 decahydro 1,4,7,10,13,16 benzohexaoxacycloocta decine ((E) 1) 17 and salts H 3 N + (CH 2 ) n NH 3 + 2ClO 4 -(C2-С6, C10, C12) 20,22,23 were synthesized according to known procedures.…”

Section: Methodsmentioning

confidence: 99%

Stereoselective [2+2] photocycloaddition in bispseudosandwich complexes of bis(18-crown-6) stilbene with alkanediammonium ions

et al. 2009

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Due to hydrogen bonding, bis(18 crown 6) stilbene forms 1 : 1, 1 : 2, and 2 : 2 complexes with H 3 N + (CH 2 ) n NH 3 + 2ClO 4 -salts (n = 2-10, 12). The length of the polymethylene chain in the diammonium ions affects the phototransformation direction of stilbene and the com position of the products. In the 2 : 2 bispseudosandwich complexes with relatively short alkanediammonium ions (n = 2-4), the stereoselective reaction of [2+2] photocycloaddition proceeds to form mainly the rctt isomer of the cyclobutane derivative. The structure of rctt cyclobutane derivative as a complex with H 3 N + (CH 2 ) 4 NH 3 + 2ClO 4 -was confirmed by X ray diffraction analysis.Stilbenes and their analogs containing the 1,2 di(aryl/ hetaryl)ethylene structural fragment are objects of numerous studies, because they possess remarkable spectral fluorescence and photochemical properties, such as the ability to reversible reactions of E-Z isomeriza tion, electrocyclization, and [2+2] photocycloaddition (PCA). 1-3 These properties were used for the creation of optoelectronic media 4 and production of multiphoton absorption materials for lasers 5 and were proposed for application in information optical recording and storage systems, 6 molecular electronic devices, switchers, and machines. 7, 8 The influence on the photochemical properties of unsaturated compounds of their self assembly to supra molecular ensembles is of considerable interest because of possibility to control the direction of photoreactions in these systems, and their stereochemical result also can often be controlled. For instance, the steroselective PCA of the stilbene derivatives can occur in cavities of cucurbit[8]uril 9 and γ cyclodextrin. 10 Stilbenes contain * Dedicated to Academician A. I. Konovalov on his 75th birthday.ing the crown ether fragment also provide a possibility of comparatively easily control of their self assembly in the presence of metal cations by complexation. 11,12Ammonium ions represent wider possibilities for fine control of the structure and photochemical properties of supramolecules, 13 including those based on crown con taining stilbenes, because the assortment of ammonium compounds is much larger than the range of inorganic substrates. For example, the formation of unusually stable donor acceptor complexes between bis(18 crown 6) stilbene ((E) 1) and diammonium derivatives of viologen analogs, which can serve as fluorescent molecular sensors to alkaline earth metal cations, was observed. 14,15 The stereospecific PCA in the dimeric complex of ammo nium containing mono(24 crown 8) stilbene was stud ied. 16 The PCA reactions of biscrown containing stilbenes can be used, for example, for the creation of new photo switchable complexing agents or systems of optical record ing of information. However, photoreactions of biscrown containing stilbenes almost have not been studied up to recently, because (to a great extent) of low availability of these compounds.

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Section: Methodsmentioning

confidence: 99%

Stereoselective [2+2] photocycloaddition in bispseudosandwich complexes of bis(18-crown-6) stilbene with alkanediammonium ions

et al. 2009

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“…4´ Formylbenzo 18 crown 6 ether was prepared according to a known procedure. 30 4 [(E) 2 (2,3,5,6,8,9,11,12,14,15 Decahydro 1,4,7,10, 13,16 benzohexaoxacyclooctadecen 18 yl)ethen 1 yl]pyridine (E 2). A mixture of 4 methylpyridine (2.87 mL, 29.4 mmol) and potassium tert butoxide, which was prepared by dissolution of potassium (0.82 g, 21 mmol) in dry tert butyl alcohol followed by concentration to dryness, in dry DMF (20 mL) was stirred at room temperature for 30 min.…”

Section: Methodsmentioning

confidence: 99%

Stereospecific solid-state [2+2] autophotocycloaddition of a styryl dye containing a 18-crown-6 fragment

et al. 2005

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A procedure was developed for the synthesis of a 18 crown 6 containing styryl dye of the pyridine series. Phototransformation products of the dye that formed upon irradiation with visible light in solution, films, and crystals were studied by 1 H and 13 C NMR spectroscopy and spectrophotometry. Irradiation of solutions of this dye in acetonitrile leads only to reversible E-Z photoisomerization of the C=C bond. Irradiation of a film of the dye induces stereospe cific [2+2] photocycloaddition to form exclusively the rctt isomer of tetrasubstituted cyclobutane. The latter was found to undergo base catalyzed isomerization giving rise to the rcct isomer. X ray diffraction study showed that photocycloaddition occurs in single crystals without their destruction. The structures of the E isomer of the dye and the resulting rctt isomer of the cyclobutane derivative were established. The characteristic features of the molecular packing of the dye favorable for topochemical photocycloaddition in the crystal and the structural changes that accompany the cyclobutane formation are discussed.

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“…The most typical photochemical processes occurring in the above selforganized systems and accompanied by considerable variation of their properties are trans-cis isomerization of the double bonds, electrocyclic reactions, and [2 + 2]-cycloaddition. Crown ether-fused stilbenes were not studied in much detail [6][7][8], though these compounds might be expected to exhibit equally interesting photochemical behavior and pronounced ability to form complexes.We recently showed that bis(18-crown-6)-stilbene Id and a number of diammonioalkyl derivatives of viologen analogs in dilute solutions give rise to unusual bi-and trimolecular complexes with effective intermolecular charge transfer due to spatial preorganization of the donor and acceptor parts of the initial molecules via hydrogen bonding [9][10][11]. Such supramolecular systems were found to be very stable; therefore, they can be regarded as convenient models for studying photoinduced intermolecular electron transfer [12] and promising species with versatile electrochemical properties [13].…”

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“…Therefore, the goal of the present work was to develop a convenient procedure for the synthesis of symmetric stilbenes containing two 12 (15,18)-crown-4(5, 6) fragments and study their structure. The first representatives of bis-crown-fused stilbenes, bis(15-crown-5)-stilbene Ic and bis(18-crown-6)-stilbene Id were synthesized by reductive dimerization of the corresponding 4-formylbenzocrown ethers with TiCl 4 and zinc in the presence of 1,8-bis-(dimethylamino)naphthalene in anhydrous tetrahydrofuran (yield 26 and 31%, respectively) [7]. A disadvantage of this procedure is the necessity of carrying out the reaction at low temperature (-70°C).…”

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Synthesis and Structure of Bis-crown-Containing Stilbenes

et al. 2005

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An improved procedure was proposed for the synthesis of stilbenes fused to two crown ether fragments at both benzene rings. The structure of new homologous symmetric bis-crown-containing stilbenes was determined by X-ray analysis. Relations were revealed between the size of the crown ether moiety and stilbene conformation in crystal and the mode of crystal packing. Conformational analysis of the prepared stilbenes in solution and in the solid state was performed by 1 H and 13 C NMR spectroscopy and by DFT quantum-chemical calculations.In the recent years, supramolecular chemistry has become one of the most extensively developing fields of organic chemistry [1]. Components of supramolecular systems are often complex and difficultly accessible organic compounds, and their synthesis in many cases constitutes the subject of a separate study. In addition, an important problem in supramolecular chemistry is prediction of properties of compounds in supramolecular systems and development of selective procedures for their self-assembly.A promising sort of molecules for studying supramolecular organization in solution, monomolecular layers, Langmuir-Blodgett films, and polymeric matrices includes crown ether-fused azobenzenes, azomethines, styryl dyes, and related compounds [2][3][4][5] possessing double N=N, C=N, and C=C bonds. Interesting properties of these compounds are the ability to form supramolecules via host-guest-like complex formation with metal and ammonium ions, considerable variations in spectral parameters due to complex formation, and the possibility of varying their structure and properties by irradiation. The most typical photochemical processes occurring in the above selforganized systems and accompanied by considerable variation of their properties are trans-cis isomerization of the double bonds, electrocyclic reactions, and [2 + 2]-cycloaddition. Crown ether-fused stilbenes were not studied in much detail [6][7][8], though these compounds might be expected to exhibit equally interesting photochemical behavior and pronounced ability to form complexes.We recently showed that bis(18-crown-6)-stilbene Id and a number of diammonioalkyl derivatives of viologen analogs in dilute solutions give rise to unusual bi-and trimolecular complexes with effective intermolecular charge transfer due to spatial preorganization of the donor and acceptor parts of the initial molecules via hydrogen bonding [9][10][11]. Such supramolecular systems were found to be very stable; therefore, they can be regarded as convenient models for studying photoinduced intermolecular electron transfer [12] and promising species with versatile electrochemical properties [13]. However, the high potential of bis-crown-containing stilbenes as building blocks for assembly of complex supramolecular systems has not been explored to a sufficient extent. One of the main reasons is relatively difficult preparation of these compounds. Therefore, the goal of the present work was to develop a convenient procedure for the synthesis of symmetric stilbenes...

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Stilbene Bis-Crown Ethers: Synthesis, Complexation and Photoisomerization.

Cited by 31 publications

References 0 publications

Stereoselective [2+2] photocycloaddition in bispseudosandwich complexes of bis(18-crown-6) stilbene with alkanediammonium ions

Stereoselective [2+2] photocycloaddition in bispseudosandwich complexes of bis(18-crown-6) stilbene with alkanediammonium ions

Stereospecific solid-state [2+2] autophotocycloaddition of a styryl dye containing a 18-crown-6 fragment

Synthesis and Structure of Bis-crown-Containing Stilbenes

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