Syntheses, cation binding, and structural properties of nitrogen-pivot lariat ethers

Date of Award




Degree Name

Doctor of Philosophy (Ph.D.)



First Committee Member

George W. Gokel, Committee Chair


A series of bibracchial lariat ethers (BiBLEs) were synthesized to survey a variety of synthetic methods and their effectiveness in preparing BiBLEs. Furthermore, this large series of BiBLEs allowed us to survey the structural features which influence binding.In order to determine the influence of increasing the number of polar donor groups, triaza-18-crown-6 and derivatives thereof were prepared. The triaza-18-crown-6 system was also chosen as a synthetic ammonium cation binder.Amphiphiles containing a cryptand binding site were prepared to study the structural features which influence molecular aggregation. The solution cloud points of certain micelles were found to be directly related to the binding ability of the cryptand. Furthermore, a direct relationship between the critical micelle concentration and the cation concentration was found.Finally, a digital simulation of the electrochemical behavior of lariat ethers was developed. We found that systems exhibiting strong binding when reduced exhibit two voltammetric waves in the presence of substoichiometric amounts of cation while systems with poor binding when reduced exhibit a single shifting wave under similar experimental conditions.


Chemistry, Organic

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