Rigidified Calixarenes Bearing Four Carbamoylmethylphosphineoxide or Carbamoylmethylphosphoryl Functions at the Wide Rim

Novel phosphinoxide-bearing ligands and their photoluminescent complexes

“…More recently, several synthetic ligands based on calixarene architecture have been developed as efficient extractants for lanthanides and actinides [7]. These ligands contained phosphinoxide groups.…”

“…These ligands contained phosphinoxide groups. Although there have been numerous papers on calixarene-phosphines and phosphinoxides [7], none of them had been dedicated to luminescence examination of their lanthanide complexes, to our knowledge. An excellent review on metal complexes, including phosphine and phosphinoxide-bearing calixarenes appeared recently [8].…”

CMPO-calix[4]arenes and the influence of structural modifications on the Eu(III), Am(III), Cm(III) separation

“…The syntheses of compounds 1 [5], 5 [16] and 9 [17] have been reported, and 6 was prepared in close analogy to a similar derivative with four (tetradecyl)ether groups [5]. Compound 2 was obtained by coupling with 3-(diphenylphosphoryl)propionic acid in the presence of PyBOP, while in the case of 3 and 4 the respective activated p-nitrophenylester (11,12) was used as acylating agent, which again was synthesized in close analogy to known examples [5]. The synthesis of the "mixed" amides 7 and 8 deserves a special mention.…”

“…The solution behaviour of these compounds is indeed not as simple as expected. Spectroscopic and solid state studies indicate that 1 forms bis-complexes [10] and polymeric assemblies [11][12][13] with trivalent lanthanide ions rather than extracting them as simple 1 : 1 species. The formation of aggregates depends on the nature of the substituents and on their location on either the wide or the narrow rim [11,12,14].…”

“…Spectroscopic and solid state studies indicate that 1 forms bis-complexes [10] and polymeric assemblies [11][12][13] with trivalent lanthanide ions rather than extracting them as simple 1 : 1 species. The formation of aggregates depends on the nature of the substituents and on their location on either the wide or the narrow rim [11,12,14]. Aggregation phenomena have a direct inBrought to you by | New York University Bobst Library Technical Services Authenticated Download Date | 5/30/15 1:08 PM fluence on the extraction processes and on the formation of a third phase [15] and a better understanding of the effects of subtle structural changes in the calixarene-CMPO derivatives could thus lead to more efficient extracting agents.…”