We sought to use light as a stimuli to regulate conformation and therefore assembly due to its ability to induce a fast response and remote activation/control without recourse to the addition of further reagents. We selected azobenzenes; commonly used photoswitches that benefit from the ability to switch rapidly and without photofatigue. Whilst unsubstituted azobenzenes are effectively photoisomerised under UV light, otetrafluorinated azobenzenes are effectively isomerised using visible light. In addition, otetrafluorinated azobenzenes have been shown to exhibit long half-lives (over 2 years) in the less thermodynamically favourable Z isomer and are synthetically accessible. , A molecule incorporating a visible light activated photoswitch and two complementary hydrogen bonding motifs would provide the key elements of a stimuli responsive synthon capable of forming a self-assembled foldamer. Opie and co-workers recently described such a scaffold I (Fig. ), comprising a central o-tetrafluorinated azobenzene moiety appended with pyridylurea (Pyr) and amidonaphthyridine (NAP) triple HBMs. These HBMs were shown to associate intramolecularly when the azobenzene adopts the Z configuration but could not engage in intermolecular hydrogen-bonding with the azobenzene in the E configuration. The asymmetry of the hydrogen-bonded heterodimerization enforced a handedness to the folding which could be biased through introduction of stereogenic centres on the backbone, however whilst the rate of photoswitching at different concentrations was assessed, concentration dependent oligomerization was not described in this prior report. Due to the relatively low Pyr•NAP dimerization affinity (Ka ~ 30 M -1 , Fig. ), We considered the possibility that formation of a supramolecular polymer from synthon I may be unlikely. Therefore, a second supramolecular synthon, based on the same photoresponsive scaffold (Fig. ), was designed. II Contained two uriedopyrmidinone (UPy), quadruple hydrogen bonding motifs. The dimerization constant for this interaction has been established to be at least Kdim ~ 6 x 10 7 M -1 (Fig. ). III Contained UPy and diamidonaphthyridine (DAN) motifs (Fig. ); the Upy•DAN dimerization affinity (Ka = 6 x 10 6