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Substituent Effects in Double‐Helical Hydrogen‐Bonded AAA‐DDD Complexes
Author(s) -
Wang HongBo,
Mudraboyina Bhanu P.,
Wisner James A.
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201103001
Subject(s) - substituent , derivatization , chemistry , hydrogen bond , hydrogen , crystallography , stereochemistry , molecule , organic chemistry , mass spectrometry , chromatography
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.