We describe a simple coordination compound of Au(I) and 6-thioguanosine, [Au(6-tGH)2]Cl, that has a rich self-assembly chemistry. In aqueous solution, the discrete complex assembles into a supramolecular fibre and forms a luminescent hydrogel at concentrations above about 1 mM. Below this concentration, the macromolecular structure is a vesicle. Through appropriate control of the solvent polarity, the gel can be turned into a lamellar film or crystallised. The molecular structure of [Au(6-tGH)2]Cl was determined using single crystal X-ray diffraction, which showed bis-6-thioguanosine linearly coordinated through the thione moiety to a central Au(I) ion. In the vesicles, the photoluminescence spectrum shows a broad, weak band at 550 nm owing to aurophilic interactions. Co-operative self-assembly from vesicle to fibre is made possible through halogen hydrogen bonding interactions and the aurophilic interactions are lost, resulting in a strong photoluminescence band at 490 nm with vibronic structure typical of an intraligand transition. The vesicle-fibre transition is also revealed by a large increase of ellipticity in the circular dichroism spectrum with a prominent peak near 390 nm owing to the helical structure of the fibres. Atomic force microscopy shows that at the same time as fibres form, the sample gels. Imaging near the vesicle-fibre transition shows that the fibres form between vesicles and a mechanism for the transition based on vesicle collisions is proposed.