1 Modular self-assembled multiporphyrin cages with tunable shape Enzo Alessio, a Massimo Casanova, a Ennio Zangrando a and Elisabetta Iengo* a a Department of Chemical and Pharmaceutical Sciences, University of Trieste, Italy. Fax: +390405583903; Tel: +390405583955; E-mail: eiengo@units.it Electronic Supplementary Information 1D and 2D NMR experiments were recorded at 500 MHz on a Varian 500 spectrometer. Proton peak positions were referenced to the peak of residual non deuterated solvent (set at δ 7.26 for CDCl 3 ). Solvents for spectroscopic measurements were of spectroscopic grade, all the other solvents were of reagent grade quality, and used as received. CDCl 3 , used in NMR experiments, was treated with basic alumina prior to use. Abbreviations: 4'-cisDPyP = 5,10-bis(4'-pyridyl)-15,20-diphenylporphyrin, 4'-transDPyP = 5,15- bis(4'-pyridyl)-10,20-diphenylporphyrin, 4'-transPyPDI = N,N'-di(4-pyridyl)-perylene-3,4:9,10- tetracarboxylic acid bisimide, tpt = 2,4,6-tris(4-pyridyl)triazine, 4'-TPyP = 5,15,10,20-(4'-pyridyl)- porphyrin, 4'-TPhPyP = 5,15,10,20-(4'-pyridylphenyl)-porphyrin. 4-(4-formylphenyl)pyridine and pyrrole were purchased from Aldrich. Metallacycle 1 was synthesized as previously reported. 9 tpt was synthesized as reported in the literature. 1S 4'-TPhPyP was synthesized according to literature procedures, via condensation of 4-(4-formylphenyl)pyridine and pyrrole. 2S Synthesis of 2 - 4: metallacycle 1 (20 mg, 1.1 × 10 -2 mmol) and tpt (5 mg, 1.65 × 10 -2 mmol) were dissolved in CHCl 3 (20 mL) and the solution was stirred at room temperature for 15 min. Concentration in vacuo to ca. 5 mL followed by addition of n-hexane induced the precipitation of 2 as a violet solid, that was isolated by filtration, washed with n-hexane and vacuum dried (21 mg, 95%). A similar procedure was followed for 3 and 4: equimolar amounts of 1 (20 mg, 1.1 × 10 -2 mmol) and 4'-TPyP (3 mg, 5.49 × 10 -3 mmol) or 4'-TPyP (5 mg, 5.49 × 10 -3 mmol) yielded 3 (22 mg, 95%) or 4 (24 mg, 95%), respectively, as a dark-violet solids. Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2012