S1 Self-assembly of a 3-D triply interlocked chiral [2]catenane Aleema Westcott, Julie Fisher, Lindsay P. Harding, Pierre Rizkallah and Michaele J. Hardie Supplementary Information Synthesis All chemicals were obtained from Sigma-Aldrich Chemical Company or Lancaster Synthesis Ltd and were used without further purification. Cyclotriguaiacylene was synthesised by literature methods. 1 4-Bromomethyl-4’-methyl-2,2’-bipyridine 2 was synthesised according to literature methods from 4,4’-dimethyl-2,2’-bipyridine in a three step procedure via 4-formyl-4’-methyl-2,2’- bipyridine 3 and 4-hydroxymethyl-4’-methyl-2,2’-bipyridine. 4 NMR spectra were recorded by automated procedures on either a Bruker DPX 300 or a Bruker ARX 250 NMR spectrometer. DOSY NMR measurements were made on a Varian Inova 500 MHz spectrometer using a 5 mm indirect detect probe. Sample temperature was maintained at 20 0 C. The pulse sequence employed was a bi-polar pulse pair simulated echo (BPPSTE) 5 operating in the ONESHOT experiment. 6 Additional parameters: number of different gradient levels, 20; gradient stabilization delay, 0.002 s; gradient length, 0.004-0.005 s; diffusion delay, 0.05 s; relaxation delay, 10 s; Kappa (unbalancing factor), 0.2. Electrospray (ES) mass spectra were measured on a Bruker MicroTOF-Q in positive ion mode. Microanalysis results were obtained from the University of Leeds Microanalytical Service. Infra-red spectra were recorded as solid phase samples on a Perkin- Elmer Spectrometer. (±)-2,7,12-trimethoxy-3,8,13-tris(4-[4’-methyl-2,2’-bipyridyl]benzyloxy)-10,15-dihydro-5H- tribenzo[a,d,g]cyclononene 1 Sodium hydride (0.3 g, 7.35 mmol) was added to a solution of cyclotriguaiacylene (0.3 g, 0.735 mmol) in anhydrous dimethylformamide (10 mL) under nitrogen, the solution was allowed to stir at room temperature for thirty minutes. 4-Bromomethyl-4’-methyl-2,2’-bipyridine 1.5 g, 5.14 mmol) was then added and the