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  • 1
    ISSN: 1573-1111
    Keywords: Crown ethers ; urea(-like) guests ; complexation ; crystal structures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The preparation and X-ray structure determinations of six complexes of urea and (O-n-butyliso)uronium salts with crown ethers are presented. Urea forms isostructural 5:1 adducts with 18-crown-6 (1) and aza-18-crown-6 (2), in which two urea molecules are each hydrogen bonded to two neighbouring hetero atoms of the macroring. The remaining urea molecules form two-dimensional layers alternating with crown ether layers. In both complexes the macroring has theg + g + a ag − a ag − a g − g − a ag + a ag + a conformation withC i symmetry. In the solid 1:1 complex of O-n-butylisouronium picrate with 18-crown-6 (3) two types of conformations of the macroring were observed: theg + g + a ag − a ag + a ag − g − ag − a ag + a conformation with approximateC m symmetry and to a lesser extent theg + g + a ag − a ag + a g + g + a ag − a ag + a conformation with approximateC 2 symmetry. Both conformations allow the guest to form three hydrogen bonds to the macrocyclic host. Three complexes of 18-crown-6 and uronium salts have been prepared and characterized by X-ray crystallography. The 1:1 complexes with uronium nitrate (4) and uronium picrate (5) both exhibit the sameC 2 conformation and the same hydrogen bonding scheme as in the least occupied form of the previous complex. A 1:2 complex with uroniump-toluenesulphonate (6) has a different hydrogen bonding scheme (two hydrogen bonds per cation to neighbouring oxygen atoms of the macroring) and a different conformation of the host molecule (theag + a ag − a ag + a ag − a ag + a ag − a conformation with almostD 3d symmetry). An attempt to prepare a solid uronium nitrate complex with diaza-18-crown-6 in the same way as the 18-crown-6·uronium nitrate (1:1) complex did not yield the expected result. Instead X-ray analysis revealed that the uronium ion is dissociated, resulting in the nitrate salt of the diprotonated diaza crown ether (7).
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0947-3440
    Keywords: Biscalix[4]arene ; Lanthanide ions ; Energy transfer ; Luminescence ; Dinuclear complexes ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three types of lower-lower rim linked biscalix[4]arenes that contain carboxylic ester (1) and/or amide functions (2 and 3) at their remaining phenolic oxygen atoms were synthesized. The homo- and heterodinuclear lanthanide ion complexes based on these ligands were used to study the energy transfer between different lanthanide ions. Photophysical studies comparing the luminescence properties of the homodinuclear Eu3+ complex and the heterodinuclear Eu3+-Nd3+ complex of 2 indicated that energy transfer is likely to occur from Eu3+ to Nd3+ with an efficiency of 〉 50%. The luminescence properties turned out to be strongly solvent dependent, which is attributed to structural changes leading to different positions of the lanthanide ions in the cavities provided by the biscalix[4]arene.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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