Supporting Information

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1 Supporting Information Hexafluorogermanate (GeFSIX) Anion-Functionalized Hybrid Ultramicroporous Materials for Efficiently Trapping of Acetylene from Ethylene Zhaoqiang Zhang, Xili Cui, Lifeng Yang, Jiyu Cui, Zongbi Bao, Qiwei Yang, Huabin Xing*, Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou , China *Correspondence to:

2 Figure S1. (A) and (B) show the pore channel structures in the diameter of 4.5 Å for ZU-32, and in the pore window size of 3.0 Å for ZU-33, respectively, along the c axes. The different nets are highlighted in gray and purple for clarity. Figure S2. (A) and (B) present the crystal structure of ZU-33 with pyridine ring tilting ca. 30 º after the solvents removed viewed from different directions. The strong C-H F hydrogen bonding induced the pyridine titling with the H-F distance of 2.35 Å. Color code: F, red; Ge, dark cyan; H, gray-25%; Cu, pink; N, blue; C, the carbon atoms in different nets are highlighted in blue and green color for clarity.

3 Figure S3. (A) and (B) present the solvent-accessible pore surface structures of ZU-32 and ZU-33, respectively, along the c axes. They show different pore channels. For ZU-32, the pore channels are with larger pore aperture size of 4.5 Å, and ZU-33 exhibits pore window size of 3.0 Å and cavity size of 4.4 Å. Figure S4. The schematic illustration of pore size of interpenetrated structures defined by F-F distance coming from two different nets.

4 Figure S5. Pore size distribution (PSD) derived from the CO 2 sorption isotherm (CO 2 at 196 K NLDFT) for ZU-32 and ZU-33. The PSD extracted from adsorption isotherms. Figure S6. Pore size distribution (PSD) derived from the N 2 sorption isotherm at 77 K NLDFT) for ZU-32.

5 Figure S7. PXRD patterns of ZU-32 (A) and ZU-33 (B) collected after the sample endured different experiments. Figure S8. The comparison of C 2 H 2 and C 2 H 4 adsorption isotherms on ZU-32 and SIFSIX-2-Cu-i collected at 298 K.

6 Figure S9. Q st of C 2 H 4 at low coverage on ZU-32. Figure S10. DFT-D calculated binding sites of C 2 H 2 (A) and C 2 H 4 (B) in SIFSIX-2-Cu-i. The different nets are highlighted by green and pink colors. Color code: F, red; Si, cyan; H-bonds, yellow broken lines. 1

7 Figure S11. (A) and (B) show the DFT-D calculated binding sites of C 2 H 4 in ZU-32. The different nets are highlighted by green and pink colors. Color code: F, red; Ge, blue; H-bonds, yellow broken lines. Figure S12. Experimental column breakthrough curves for C 2 H 2 and C 2 H 4 (50/50) separations with ZU-32, ZU-33, SIFSIX-2-Cu-i and SIFSIX-3-Zn. (gas flow: 1.25 ml min -1 )

8 Figure S13. Cycling column breakthrough tests for C 2 H 2 /C 2 H 4 (1/99) mixtures separation with ZU-32 (A) and ZU-33 (B) at 298 K and 1.01 bar. (Flow rate: 1.25 ml min -1 ) Figure S14. Schematic illustration of the apparatus for the breakthrough experiments.

9 Table S1. Comparison of the adsorption uptakes for C 2 H 2 and C 2 H 4 in several similar materials. Materials Pore volume (cm 3 g -1 ) BET (m 2 g -1 ) C 2 H 2 uptake at 0.01 bar (cm 3 cm -3 ) C 2 H 2 uptake (cm 3 cm -3 ) C 2 H 4 uptakes (cm 3 cm -3 ) ZU ZU SIFSIX-2-Cu-i a SIFSIX-14-Cu-i a calculated from N 2 isotherms at 77 K BET surface area calculated from CO 2 isotherms at 196 K The C 2 H 2 and C 2 H 4 uptake were collected at 298 K and 1 atm. Table S2. Dual-site Langmuir-Freundlich parameter fits for C 2 H 2 and C 2 H 4 in ZU-32 and ZU-33. Site A Site B q A,sat b A0 v A q B,sat b B0 v B mol kg -1 Pa -va mol kg -1 Pa -vb ZU-32 C 2 H C 2 H ZU-33 C 2 H C 2 H Reference: (1) Cui, X. L.; Chen, K. J.; Xin, H. B.; Yang, Q. W.; Krishna, R.; Bao, Z. B.; Wu, H.; Zhou, W.;

10 Dong, X. L.; Han, Y.; Li, B.; Ren, Q. L.; Zaworotko, M. J.; Chen, B. L., Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene. Science 2016, 353, (6296), 141. (2) Li, B.; Cui, X. L.; O'Nolan, D.; Wen, H. M.; Jiang, M. D.; Krishna, R.; Wu, H.; Lin, R. B.; Chen, Y. S.; Yuan, D. Q.; Xing, H. B.; Zhou, W.; Ren, Q. L.; Qian, G. D.; Zaworotko, M. J.; Chen, B. L., An ideal molecular sieve for acetylene removal from ethylene with record selectivity and productivity. Adv. Mater. 2017, 29, (47),