Substituent effects in double-helical hydrogen-bonded AAA-DDD complexes |
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Authors: | Wang Hong-Bo Mudraboyina Bhanu P Wisner James A |
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Affiliation: | Department of Chemistry, The University of Western Ontario, 1151 Richmond St., London, ON, N6A 5B7, Canada. |
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Abstract: | Two series of DDD and AAA hydrogen-bond arrays were synthesized that form triply-hydrogen-bonded double-helical complexes when combined in CDCl(3) solution. Derivatization of the DDD arrays with electron-withdrawing groups increases the complex association constants by up to a factor of 30 in those arrays examined. Derivatization of the AAA arrays with electron donating substituents reveals a similar magnitude effect on the complex stabilities. The effect of substitution on both types of arrays are modeled quite satisfactorily (R(2) > 0.96 in all cases) as free energy relationships with respect to the sums of their Hammett substituent constants. In all, the complex stabilities can be manipulated over more than three orders of magnitude (>20 kJ mol(-1)) using this type of modification. |
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Keywords: | helical structures hydrogen bonds linear free energy relationships self‐assembly supramolecular chemistry |
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