1. Principles of Chemical Recognition and Transport in Extractive Separations: Synthesis of Dibenzo-14-Crown-4 Ethers Bearing Fluoroalcohol Lariats Peter V. Bonnesen*, Frederick V. Sloop Jr., Tamara J. Haverlock, and Bruce A. Moyer Chemical Separations Group, Chemical Sciences Division Oak Ridge National Laboratory, Oak Ridge, TN 37831-6119 2003 DOE Separations and Heavy Element Chemistry Contractors’ Meeting Sante Fe, New Mexico April 29, 2003

2. DB14C4 forms “sandwich” complex with Na + Crystal structure of (DB14C4) 2 NaClO42CHCl 3 obtained by J. C. Bryan

3. Molecular tweezers? Could lariats with H-bond donor groups appended as shown interact with the anion upon self-assembly of the sandwich?

4. What kinds of lariats should we use?  Presence of electron-withdrawing fluorine atoms increases electropositive character of alcohol proton  Good H-bond donors.  In addition, alcohol oxygen basicity is decreased, reducing tendency for fluorinated alcohols to form H-bond networks with each other. Alcohols with fluorinated side groups are attractive:

5. n = 1 or 2 How do we make these?

6. Successful synthetic strategy For details, see poster

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