Solvent-induced switching between two supramolecular assemblies of a guanosine–terthiophene conjugate

Abstract

We report here our findings on a lipophilic guanosine derivative armed with a terthiophene unit that undergoes a pronounced variation of its supramolecular organisation by changing the polarity of the solvent. In chloroform the guanosine derivative, templated by alkali metal ions, assembles via H-bonding in G-quartet based D₄-symmetric octamers; the polar guanine bases are located into the inner part of the assembly and act as a scaffold for the terthienyl pendants. On the other hand, in the more polar (and H-bond competing) acetonitrile, different aggregates are observed in which the terthiophene chains are π–π stacked in a helicoidal (left-handed) arrangement in the central core, and the guanine bases (free from hydrogen bonding) are located at the periphery and exposed to the solvent. The system can be switched back and forth by subsequent addition of chloroform and acetonitrile. The solvent-induced switching can be easily followed by circular dichroism spectroscopy: the CD exciton-couplet in the guanine chromophore absorption region observed in chloroform disappears after addition of acetonitrile, indicating the disassembly of the G-quartet based octameric structure, while an intense quasi-conservative exciton splitting in the 300–450 nm spectral region becomes predominant in the CD spectrum. This latter strong bisignate optical activity can be ascribed to the helical packing of conjugated terthiophene moieties stabilised by π–π interactions. NMR spectra and photophysical investigations confirm the structures of the guanine-directed and thiophene-directed assemblies in chloroform and acetonitrile, respectively.