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The formation of guanine quartets with 9-isopropylguanine ((i)PG) is discussed in organic solvents. Crystal structures of the (i)PG quartets were determined by X-ray crystallography with template cations (Na(+) and Ca(2+)) and the structure without a template cation was also obtained by virtue of the stabilization by intermolecular hydrogen bonding with water molecules of crystallization. The difference in the quartet formation of (i)PG in the presence and absence of a template cation was clearly demonstrated by (1)H NMR measurements in CDCl(3)-CH(3)OH mixed solvents. The quartet formation is mainly governed by the enthalpy gain due to the electrostatic interaction between the O6 oxygen in (i)PG and the template cations in the presence of the cations rather than the intermolecular hydrogen bonding, while desolvation of (i)PG is the dominant factor for the formation in the absence of cations. In the presence of Na(+) and Ca(2+), ΔH and ΔS values in the formation of (i)PG-4-Na(+) and (i)PG-4-Ca(2+) complexes were determined to be ΔH = -8.4 kcal mol(-1) and ΔS = +50 cal mol(-1) K(-1) for Na(+) and ΔH = -12.9 kcal mol(-1) and ΔS = +34 cal mol(-1) K(-1) for Ca(2+) on the basis of van't Hoff plots attained from the results of temperature-dependent UV-Vis spectroscopic measurements.

Formation of a π-π stacked assembly between a Na(+)-templated G-quartet and octaethylporphyrinatonickel(II) was observed by spectroscopic methods in methanol/chloroform and the formation dynamics of the assembly was elucidated.