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Objective

Molecular Recognition by Picolylamine-Based Tripodal Ligands and Its Application in Sensing and Asymmetric Catalysis Amanda Mickley, 1 Patrick Carney, 1 Steven Lopez, 2 Jennifer Lee, 2 and Zhaohua Dai 1,* Chemistry Departments of Pace University (1) and New York University (2). Objective.

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Objective

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  1. Molecular Recognition by Picolylamine-Based Tripodal Ligands and Its Application in Sensing and Asymmetric CatalysisAmanda Mickley,1 Patrick Carney,1 Steven Lopez,2Jennifer Lee,2 and Zhaohua Dai1,*Chemistry Departments of Pace University (1) and New York University (2)

  2. Objective • Improve the selectivity in the detection of Hg(II) through a stereochemical approach which systematically employs chiral podand, piperidine bearing ligands sulfur atoms; • Improve Hg(II) sensing sensitivity by using circularly polarized fluorescence excitation (CPE); • Systematically develope Fe(II) complexes of TPA-based chiral podands, piperidines and quinuclidines as green asymmetric catalysts for better product control and prediction in alkane hydroxylation by H2O2. Elucidate its mechanism • Elucidate mechanism to facilitate the better understanding of the interactions operating the above-mentioned molecular recognition events

  3. Chiroptical Fluorescence Sensors for Mercury

  4. 1st Genearation Sensor for MercuryRatiometric Fluorescent Sensor Hg2+

  5. Chiroptical Response HgII CuII CH3

  6. Pattern Recognition: Signal Selectivity Hg2+ -1

  7. Next Generation Sensors for Hg2+ We intend to use these ligands to further develop circularly polarized fluorescence excitation (CPE), which is based on fluorescence-detected circular dichroism, which gives better contrast and eliminates many spectral interferences.

  8. + hydrolysis 1.

  9. Alkane Hydroxylation • Converting saturated C-H bonds directly into alcohols • Important to synthetic organic chemistry, fuel industry and other industries using petrochemical feed stock • Helpful in modeling electron-transfer processes in biological systems, and producing new catalysts

  10. Fe(II)-TPA as Catalysts Ligands: Achiral; Complexes: Octahedral • Products: Regio-selective, Diastereo-selective • Not enantio-selective K. Chen and L. Que, Jr, JACS, 2001, 123, 6327

  11. Rigidification Enhances Enantiomeric and Regional Selectivity M. S. Chen, M. C. White. Science, 2007, 318, 783.

  12. Our Approach Make Chiral Ligands and use their Fe-(II) complexes as catalysts Systematically rigidify the chiral ligand to improve enantio- and regio- selectivity Put Br on ligands to increase reactivity according DFT calculation Chiral podand piperidine quinuclidine

  13. Podand and Piperidine Ligands

  14. Synthesis of Quinuclidines

  15. SSS-29

  16. SSS-29 Purity and Cu(II) Complex

  17. Acknowledgement • Prof. James Canary (NYU) • Prof. Demosthenese Athanasoupolos (Pace) • Kirill Grinberg (Midwood High School) Funding: ACS Petroleum Research Fund Research Corporation for Science Advancement Pace University Scholarly Research Fund Pace University Kenan Faculty Development Fund

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