Supporting information New Approach towards Zeolitic Tetrazolate-Imidazolate Frameworks (ZTIFs) with Uncoordinated N-heteroatom Sites For high CO2 Uptake

Materials and general procedures. All of the chemicals are commercial available, and used without further purification. Elemental analyses of C and H were performed with an EA1110 CHNS-0 CE elemental analyzer. The IR (KBr pellet) spectra were recorded (400-4000 cm-1 region) on a Nicolet Magna 750 FT-IR spectrometer. Thermogravimetric analyses (TGA) were carried out in an air atmosphere with a heating rate of 10 o C/min on a STA449C integration thermal analyzer. Powder X-ray diffraction (PXRD) data were collected on a Rigaku MultiFlex diffractometer using Cu Kα radiation. 1 HNMR experiments were carried out on a Bruker spectrometer operating at resonance frequencies of 400 MHz. Inductively Coupled Plasma OES (ICP-OES) was performed on ULTIMA 2 ICP OES Spectrometer (Jobin Yvon, France). The N 2 adsorption isotherms were recorded by using a micromeritics ASAP 2020 surface area and porosity analyzer. The structure of ZTIFs were solved by direct methods and refined on F 2 by full-matrix, least-squares methods using the SHELXL-97 program package. Synthesis of Zn(5-mtz)(2-eim). x(guest) (ZTIF-1): The mixture of Zn(CH 3 CO 2) 2 ·2(H 2 O) (0.5 mmol, 0.110 g), 5-methyltetrazole (5-mtz, 0.5 mmol, 0.043 g), 2-ethylimidazole (2-eim, 0.5 mmol, 0.48 g) in DMF (2 ml) and ethanol (2ml) was sealed in a 20 ml vial and heated to 120 o C for 3 days, and then cooled to room-temperature. The yellow polyhedral crystals were obtained, washed with ethanol, and dried at room temperature (Yield: 50%). The micro-synthesis condition of ZTIF-1 can be scalable to 1 gram scale by using the same reaction conditions in a larger volume (50 mL Teflon-lined stainless steel reactor). The coexistence of 5-mtz and 2-eim in ZTIF-1 are proved by 1 H NMR. To prove the phase purity of the bulk sample, the powder-XRD (PXRD) and elemental analysis (EA) of the activated samples are presented here. A comparison calculated/found EA of the activated samples proved the phase purity of the sample. The ratio of these two ligands has been obtained from the EA results.