Solvent-Induced High Fidelity Switching Between Two Discrete Supramolecules

Abstract

Here we show the reversible high fidelity switching between two discrete self-assembled supramolecules made from a lipophilic 8-phenyl-2'-deoxyguanosine derivative induced by an indirect solvent effect. A hexadecameric supramolecule containing four stacked tetramers is formed in acetonitrile aided by higher potassium concentrations. When the amount of weakly solvated potassium decreases, due the lower activity of potassium iodide in chloroform, an octamer is formed after the dissociation of the two outer tetramers in the hexadecamer. The switching process results from an unprecedented subtle interplay between the activity of potassium iodide and the steric crowding within the self-assembled structure. Besides the possible applications in nanoconstruction, this phenomenon sheds light into the mechanism of formation of self-assembled supramolecules made from guanosine derivatives.

Tuning Thermoresponsive Supramolecular G-Quadruplexes

“…44 On the other hand, the slight decrease in T m is related to the increased steric repulsion within the aforementioned SGQs resulting from ethoxy ( 2 ), ethylamino ( 3 ), and methyl ( 1 ) groups, which destabilize the assemblies of the former two relative to the latter. 39 …”

Hydrogen‐Bonding Directed Assembly and Gelation of Donor–Acceptor Chromophores: Supramolecular Reorganization from a Charge‐Transfer State to a Self‐Sorted State

“…[18] The CGC value for DAN-4 was found to be 2 mm (Table 1), which is almost four times lower than that in TCE (Table 1), and the T g (20 mm) was found to be 65 8C, which is more than twice as much as that in TCE (Table 1). Similarly for NDI-2 also the gelation data indicates stronger self-assembly compared to that in TCE; this fact can be attributed to stronger hydrogen-bonding interaction in hydrocarbon solvent.…”

Self-assembled cation transporters made from lipophilic 8-phenyl-2′-deoxyguanosine derivatives

“…Specifically, the thermodynamic stability, molecularity and fidelity of such supramolecules is influenced by parameters such as: (a) the nature and the position of the functional group at the 8-phenyl ring,14, 15 and (b) the nature and the size of the moieties attached to the 3'- and 5'-OH groups of the furanose ring 16,17. The medium, or extrinsic parameters, also influences the assembly process 18,19. For example, in organic media, and under identical conditions, the meta -acetylphenyl derivative ( mAGi ) assembles into a hexadecamer, while its para acetylphenyl isomer ( pAGi ) assembles into an octamer (Figure 1).…”