Synthesis and self-association of double-helical AADD arrays.

The design and syntheses of four self-complementary oligomers that contain an underlying AADD hydrogen bond sequence are presented, and their self-association was examined in the solution and solid state. The molecular recognition between the two strands is highly sensitive to substitutions of their component heterocycles. Substitution with electron-donating and -withdrawing groups and the influence of preorganization has a large effect on the overall stabilities of the complexes studied. In particular, a wide range (>10(5) M(-1)) of stabilities with respect to substitutions at various positions in the AADD oligomers was demonstrated. In the most extreme case, the dimerization constant measured (K(dimer) ≥4.5×10(7) M(-1)) is comparable to the most stable homodimers of neutral AADD arrays reported to date.