TY - JOUR
T1 - Self-assembled ionophores from isoguanosine: diffusion NMR spectroscopy clarifies cation's and anion's influence on supramolecular structure
AU - Evan-Salem, Tamar
AU - Frish, Limor
AU - van Leeuwen, F.W.B.
AU - Reinhoudt, David
AU - Verboom, Willem
AU - Kaucher, Mark S.
AU - Davis, Jeffery T.
AU - Davis, J.T.
AU - Cohen, Yoram
PY - 2007
Y1 - 2007
N2 - Cation-templated self-assembly of the lipophilic isoguanosine (isoG 1) with different monovalent cations (M+=Li+, Na+, K+, NH4+, and Cs+) was studied in solvents of different polarity by using diffusion NMR spectroscopy. Previous studies that did not use diffusion NMR techniques concluded that isoG 1 forms both pentamers (isoG 1)5M+ and decamers (isoG 1)10M+ in the presence of alkali-metal cations. The present diffusion NMR studies demonstrate, however, that isoG 1 does not form (isoG 1)5M+ pentamers. In fact, the diffusion NMR data indicates that both doubly charged decamers of formula (isoG 1)102 M+ and singly charged decamers, (isoG 1)10M+, are formed with lithium, sodium, potassium, and ammonium tetraphenylborate salts (LiB(Ph)4, KB(Ph)4, NaB(Ph)4 and NH4B(Ph)4), depending on the isoG 1:salt stoichiometry of the solution. In the presence of CsB(Ph)4, isoG 1 affords only the singly charged decamers (isoG 1)10Cs+. By monitoring the diffusion coefficient of the B(Ph)4- ion in the different mixtures of solvents, we also concluded that the anion is more strongly associated to the doubly charged decamers (isoG 1)102 M+ than to the singly charged decamers (isoG 1)10M+. The (isoG 1)102 M+ species can, however, exist in solution without the mediation of the anion. This last conclusion was supported by the finding that the doubly charged decamers (isoG 1)102 M+ also prevail in 1:1 CD3CN:CDCl3, a solvent mixture in which the B(Ph)4- ion does not interact significantly with the self-assembled complex. These diffusion measurements, which have provided new and improved structural information about these decameric isoG 1 assemblies, demonstrate the utility of combining diffusion NMR techniques with conventional NMR methods in seeking to characterize labile, multicomponent, supramolecular systems in solution, especially those with high symmetry.
AB - Cation-templated self-assembly of the lipophilic isoguanosine (isoG 1) with different monovalent cations (M+=Li+, Na+, K+, NH4+, and Cs+) was studied in solvents of different polarity by using diffusion NMR spectroscopy. Previous studies that did not use diffusion NMR techniques concluded that isoG 1 forms both pentamers (isoG 1)5M+ and decamers (isoG 1)10M+ in the presence of alkali-metal cations. The present diffusion NMR studies demonstrate, however, that isoG 1 does not form (isoG 1)5M+ pentamers. In fact, the diffusion NMR data indicates that both doubly charged decamers of formula (isoG 1)102 M+ and singly charged decamers, (isoG 1)10M+, are formed with lithium, sodium, potassium, and ammonium tetraphenylborate salts (LiB(Ph)4, KB(Ph)4, NaB(Ph)4 and NH4B(Ph)4), depending on the isoG 1:salt stoichiometry of the solution. In the presence of CsB(Ph)4, isoG 1 affords only the singly charged decamers (isoG 1)10Cs+. By monitoring the diffusion coefficient of the B(Ph)4- ion in the different mixtures of solvents, we also concluded that the anion is more strongly associated to the doubly charged decamers (isoG 1)102 M+ than to the singly charged decamers (isoG 1)10M+. The (isoG 1)102 M+ species can, however, exist in solution without the mediation of the anion. This last conclusion was supported by the finding that the doubly charged decamers (isoG 1)102 M+ also prevail in 1:1 CD3CN:CDCl3, a solvent mixture in which the B(Ph)4- ion does not interact significantly with the self-assembled complex. These diffusion measurements, which have provided new and improved structural information about these decameric isoG 1 assemblies, demonstrate the utility of combining diffusion NMR techniques with conventional NMR methods in seeking to characterize labile, multicomponent, supramolecular systems in solution, especially those with high symmetry.
KW - METIS-241412
KW - Supramolecular Chemistry
KW - Self-Assembly
KW - Anions
KW - IR-72333
KW - isoguanosine
KW - diffusion NMR spectroscopy
KW - cations
U2 - 10.1002/chem.200601015
DO - 10.1002/chem.200601015
M3 - Article
SN - 0947-6539
VL - 13
SP - 1969
EP - 1977
JO - Chemistry : a European journal
JF - Chemistry : a European journal
IS - 7
ER -