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Design and Development of 2-Functionalized Calix[4]arenes and Their Investigation in the Separation of Lanthanides

Menon, Sreejit Rajiv, Menon
http://rave.ohiolink.edu/etdc/view?acc_num=toledo1461715995

Abstract Details

2016, Doctor of Philosophy, University of Toledo, Chemistry.
The rare earth elements (REE), composed primarily of the fifteen lanthanides, find broad application in many modern devices making them indispensable and important to the sustainable, green world approach prevalent these days. Liquid-liquid extraction for the separation of lanthanides using a calix[4]arene scaffold with coordinating ligands on its lower rim has been studied for many years. New solid phase materials capable of coordinating metals are important to the field of rare earth metal separation and isolation as they will not only minimize solvent wastes but have the potential to be reused, thereby making the separation and recovery of rare earth metals economical. In the first part, the synthesis and characterization of new chlorine terminated 2-alkyl-p-tert-butylcalix[4]arenes with different coordinating ligands such as phosphine oxides, ketones, CMPO, and esters on the lower rim were investigated. Here, the extraction efficiencies of these new calix[4]arenes for rare earth metals in liquid-liquid extraction was investigated in order to confirm that functionalization at the 2-position of the calix[4]arenes does not interfere with the extraction properties of the coordinating ligands on the lower rim. In the second part of this project, further modification of the 2-position was carried out by converting the chlorine terminated end to the highly desirable amino group, which was then utilized in coupling reactions to immobilize these 2-position/tail modified calix[4]arenes bearing lower rim coordinating ligands on solid supports covalently via the attached linker group. These newly synthesized solid phase extractants were characterized using solid state NMR spectroscopy, FT-IR spectroscopy, elemental analysis and EDS and their thermal stability was further determined using TGA. This represents the first report of attachment of calix[4]arene ligands to solid supports via their 2-positions to the best of our knowledge. These new materials were further investigated in the separation of lanthanides.
Joseph Schmidt, Dr. (Advisor)
Mark Mason, Dr. (Committee Member)
Steven Sucheck, Dr. (Committee Member)
Constance Schall, Dr. (Committee Member)
159 p.
Chemistry
Calixarenes; lanthanides; separation; liquid-liquid extraction; solid phase extraction;

Recommended Citations

Citations

  • Menon, Menon, S. R. (2016). Design and Development of 2-Functionalized Calix[4]arenes and Their Investigation in the Separation of Lanthanides [Doctoral dissertation, University of Toledo]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=toledo1461715995

    APA Style (7th edition)

  • Menon, Menon, Sreejit. Design and Development of 2-Functionalized Calix[4]arenes and Their Investigation in the Separation of Lanthanides. 2016. University of Toledo, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=toledo1461715995.

    MLA Style (8th edition)

  • Menon, Menon, Sreejit. "Design and Development of 2-Functionalized Calix[4]arenes and Their Investigation in the Separation of Lanthanides." Doctoral dissertation, University of Toledo, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=toledo1461715995

    Chicago Manual of Style (17th edition)

toledo1461715995
971
© 2016, all rights reserved.
This open access ETD is published by University of Toledo and OhioLINK.