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1 Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers. This journal is the Partner rganisations 2018 A ligand conformation preorganization approach to construct a copper-hexacarboxylate framework with a novel topology for selective gas adsorption Yao Wang, a Minghui He, a Xiaoxia Gao, a Xia Wang, a Guohai Xu, b* Zhengyi Zhang c and Yabing He a* a Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Life Sciences, Zhejiang ormal University, Jinhua , China. heyabing@zjnu.cn b Key Laboratory of Jiangxi University for Functional Materials Chemistry, School of Chemistry and Chemical Engineering, Gannan ormal University, Ganzhou, Jiangxi , China. xugh308@gnnu.cn c Bruker (Beijing) Scientific Technology Co., Ltd., Beijing , China

2 Fig. S1 The electronic photograph of the as-synthesized ZJU-100.

3 Fig. S2 (a) The simulated (black) and experimental (red) PXRD patterns of ZJU-100; (b) the PXRD patterns of ZJU-100 after immersion in aqueous HCl/aH solutions with ph ranging from 3 to 12 for 24 h.

4 Weight (%) 100 ZJU T ( o C) Fig. S3 The TGA curve of ZJU-100 under nitrogen atmosphere.

5 Transmittance (cm -1 ) Wavenumber (cm -1 ) ligand ZJU-100 Fig. S4 Comparison of FTIR spectra of ZJU-100 and its corresponding ligand H 6 L.

6 S BET = 1/( )/ = 1933 m 2 g -1 S Langmuir = (1/ )/ = 2113 m 2 g -1 BET constant C = / = 1460 ( p/ p o ) nm 1 C 1 = Fig. S5 (a) The consistency, (b) BET surface area, and (c) Langmuir surface area plots for ZJU-100.

7 Fig. S6 (a) 2 isotherms at 77 K and (b) DFT pore size distributions of ZJU-100 before and after immersion in water at room temperature for 24 h.

8 Fig. S7 Comparison of the pure-component isotherm data for (a) C 2 H 2, (b) C 2, and (c) CH 4 in ZJU-100 with the fitted isotherms at 278 K, 288 K, and 298 K.

9 H 3 CC CCH 3 H 3 C CH 3 H 3 CC CCH 3 CH 3 CCH 3 CCH ppm H 3 C CH 3 CH ppm

10 ppm ppm Fig. S8 1 H and 13 C MR spectra.

11 Table S1 Crystal data and structure refinement for ZJU-100. MFs ZJU-100 Empirical formula C 297 H 162 Cu Formula weight λ (Å) Crystal system Hexagonal Space group P6/mmm a = (15) Å b = (15) Å Unit cell dimensions c = (7) Å α = 90 o β = 90 o γ = 120 o V (Å 3 ) 89240(5) Z 6 D c (g cm -3 ) μ (mm -1 ) F(000) θ range for data collection ( o ) to h 76 Limiting indices -76 k l 26 Reflections collected / unique / R int Refinement method Full-matrix least-squares on F 2 Data/restraints/parameters / 3472 / 1204 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = wr 2 = R indices (all data) R 1 = wr 2 = Largest diff. peak and hole (e. Å -3 ) and CCDC

12 Table S2 Summaries of gas adsorption properties and pore textural parameters of some reported MFs based on triisophthalate ligands. MFs Metal ion Ligand structure S BET (m 2 g -1 ) V p (cm 3 g -1 ) C 2H 2 uptake (cm 3 g -1, STP) C 2 uptake (cm 3 g -1, STP) Ref. Zn 4(BHB) Zn A A 35 (273 K, 1 atm) 1 CH 3 SDU-1 Zn 2+ H 3C CH A A 2, 3 CH 3 PC-5 Co 2+ H 3C CH A A 2 UTSA-20 Cu (296 K, 1 atm) 82.4 (296 K, 1 atm) 4, 5 ZJU-100 Cu 2+ CH 3 H 3C CH (298 K, 1 atm) 83.1 (298 K, 1 atm) This work Cu-TDPAT Cu 2+ H H H (298 K, 1 atm) 132 (298 K, 1 atm) 6, 7 Cu-TDPAH Cu 2+ H H H (298 K, 1 atm) 116 (298 K, 1 atm) 8 MFM-132 Cu A A 9 SDU-8 Cu 2+ Si A A 10 i Bu SDU-7 Cu 2+ Si A A 10 GDMU-2 Cu A 74 (273 K, 1 bar) 11

13 SDU-6 Cu 2+ Si A A 10 H H Cu-TPBTM Cu 2+ H A A 12 H H Cu 3(BTB 6- ) Cu 2+ H A A 13 H H Cu 3(TATB 6- ) Cu 2+ H A A 13 H TU-105 (U-125) (TT-122) Cu A 187 (273 K, 1 atm) H HUST-5 Cu 2+ H H A 56 (298 K, 1 bar) 17 TT-112 Cu A A 18 Cu-TTA Cu 2+ H H H A 65.5 (298 K, 800 Tor) 19 TT-119 (PC-69) Cu A A 20, 21 PMF-2 (PC-61) Cu A A A 22, 23 PC-66 Cu A A 22

14 PC-68 Cu A A 22 U-100 (PC-610) Cu A A 22, 24 U-110 Cu A A 25

15 Table S3 Langmuir-Freundlich parameters for adsorption of C 2 H 2, C 2, and CH 4 in ZJU-100. Guest q sat (mmol g -1 ) b 0 (kpa) -v E (kj mol -1 ) v R 2 C 2 H C CH

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