Strain-promoted ‘click’ Modification of a Mesoporous.pdf

S1 Support Information for Strain-promoted ‘click’ Modification of a Mesoporous Metal-Organic Framework Chong Liu, Tao Li, Nathaniel L. Rosi* Department of Chemistry, University of Pittsburgh, 219 Parkman Ave., Pittsburgh, PA 15260 Contents: 1. General Procedures 2. Synthesis of 2-azido-4,4’-biphenyl dicarboxylic acid 3. Synthesis of N3-bio-MOF-100 and characterization 4. Synthesis of DIBAC derivatives 5. Strain-promoted click reactions for 1 2 and characterization 6. Thermogravimetric analysis (TGA) 7. Copper-catalyzed click reactions for1-hexyne and characterization 8. Strain-promoted click reaction for 3 and peptide coupling 9. Additional images S2 1. General procedures All purchased chemicals were used without further purification. The elemental analyses (EA) were performed by the University of Illinois, Department of Chemistry Microanalysis Laboratory using an Exeter Analytical CE440. X-ray powder diffraction patterns were collected using a Bruker AXS D8 Discover powder diffractometer at 40 kV, 40 mA for Cu Kα, (λ = 1.5406 ?) with a scan speed of 0.20 sec/step from 2.5 to 20 o at a step size of 0.02 o. 1H-NMR and 13C-NMR spectra were obtained using a Bruker Avance III 400 MHz and 500 MHz spectrometers. Chemical shifts are in parts per million using the residual solvent peak (Chloroform-d and DMSO-d6) as the reference value. Liquid chromatography-mass spectrometry (LCMS) analyses were performed on a Shimadzu LCMS-2020. Two LC methods were employed both using water and acetonitrile eluents. In the first method, the flow rate was held steady at 0.2 mL/min and acetonitrile was increased steadily from 10 % to 90 % over 0-9 min and then reduced to 10% acetonitrile for the final minute. In the second method, the flow rate was held steady at 0.2 mL/min and the acetonitrile:water ratio was held constant at 1:1 for the entire 6 min running time. The ionization interface was simultaneous ESI