Supporting Information (98 pages)

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1 Supporting Information (98 pages) Introduction of Functionality, Selection of Topology, and Enhancement of Gas Adsorption in Multivariate Metal Organic Framework-177 Yue-Biao Zhang, Hiroyasu Furukawa, Nakeun Ko, Weixuan Nie, Hye Jeong Park, Satoshi Okajima, Kyle E. Cordova,, Hexiang Deng,*,, Jaheon Kim,*, and Omar M. Yaghi*,, Department of Chemistry, University of California Berkeley, Materials Sciences Division, Lawrence Berkeley National Laboratory, and Kavli Energy NanoSciences Institute, Berkeley, California 94720, United States Department of Chemistry, Soongsil University, Seoul , Republic of Korea College of Chemistry and Molecular Sciences, Wuhan University, Wuhan , P. R. China Center for Molecular and NanoArchitecture, Vietnam National University, Ho Chi Minh City , Vietnam King Abdulaziz City for Science and Technology, Riyadh 11442, Saudi Arabia Table of Contents Section S1. Syntheses of Organic Linkers S2 Section S2. Single-crystal X-ray Diffraction Analyses S14 Section S3. Powder X-ray Diffraction Analyses S49 Section S4. Thermal Gravimetric Analyses S62 Section S5. 1 H NMR Spectroscopy S74 Section S6. Low-pressure gas adsorption measurements S85 References S98 S1

2 Section S1. Syntheses of Organic Linkers The syntheses of the acid forms of BTB derivative organic linkers with various functional groups were all based on the palladium-catalyzed Suzuki Miyaura cross-coupling reactions to produce their ester forms with further saponification and acidification. There are two routes to synthesize the ester form of organic linkers: (1) Synthesize different (4-(methoxycarbonyl)phenyl)boronic acids (or their pinacol esters) with desired functional group on them, and further coupling with 1,3,5-tribromobenzene; (2) Synthesize the 1,3,5-tris(boronic pinacol ester)benzene, 1 and coupling with different functionalized 4-bromobenzoate esters, 2 which are more commercial available leading to less synthetic works in the lab. In this work, we actually used both routes depending on the convenience of getting the functionalized (4-(methoxycarbonyl)phenyl)boronic acids (or their pinacol esters), but most of them can be synthesized adopting the synthetic route 2. Br Br O O + B B O O Br PdCl 2(dppf)/KOAc DMF(anhydrous) O B O O O B 1 (98% yield) O B O PdCl 2(dppf)/CsF 2:1 p-dioxane/h 2 O COOMe NH 2 COOMe OMe F COOMe F COOMe COOMe F COOMe Me Br Br Br Br Br Br COOMe NH 2 F COOMe F COOMe F H 2 N F F F MeOOC COOMe MeOOC COOMe NH 2 F F MeOOC F COOMe (48% yield) COOMe OMe (55% yield) COOMe (48% yield) COOMe Me MeO Me MeOOC COOMe OMe MeOOC COOMe MeOOC Me COOMe (54% yield) (47% yield) (43% yield) Scheme S1. Syntheses of organic linkers based on Suzuki Miyaura cross-coupling reactions. S2

3 Synthesis of Compound 1: Anhydrous DMF (10 ml) was purged with N 2 and then transferred via a cannula into a three-neck round bottomed flask charged with 1,3,5-tribromobenzene (1.00 g, 3.17 mmol) and bis(pinacolato)diboron (2.54 g, 9.53 mmol). Potassium acetate (1.87 g, 19.0 mmol) and Pd(dppf)Cl 2 (0.087 g, 0.12 mmol) were then quickly added into the flask. The resulting mixture was stirred vigorously and heated at 90 C for 24 hours. After cooling down to room temperature, deionized water (120 ml) was added. Black precipitate was collected by filtration, and washed with deionized water three times, which was dried under vacuum (98% yield). Synthesis of Compound 2: A mixture of compound 1 (0.79 g, 1.7 mmol) and methyl 2-amion-4-bromonbenzoate (1.35 g, 5.88 mmol) was dissolved in 48 ml mixed solvent of p-dioxane/h 2 O (1:1 v/v), which was deoxygenated by three freeze-pump-thaw cycles and protected under N 2 atmosphere. After quickly adding of CsF (2.40 g, 15.7 mmol) and Pd(dppf)Cl 2 (0.095 g, 0.13 mmol), the suspension was heated and stirred vigorously at 90 C for 24 hours. After cooling down to room temperature, the resulting suspension was added with 150 ml of 20% NH 4 Cl solution, and extracted three times with 3 50 ml EtOAc using a 250-mL separatory funnel. The organic layers were combined, washed with saturated brine, dried with anhydrous Na 2 SO 4 and filtered. A crude product was obtained after removing all the solvent by rotary evaporation, and further purified by quick chromatography using CH 2 Cl 2 /EtOAc (15:1 v/v) as eluent (48% isolated yield). 1 H NMR (400 MHz, DMSO-d 6, δ): 7.85 (s, 3H, Ar H), 7.83 (d, J = 8.4 Hz, 3H, Ar H), 7.24 (s, 3H, Ar H), 7.00 (d, J = 8.4 Hz, 3H, Ar H), 6.75 (s, 6H, NH 2 ), 3.82 (s, 9H, -COOCH 3 ). Synthesis of linker B: Compound 2 (0.443 g, mmol) was dissolved in 27 ml THF, added with 0.5 M NaOH aqueous solution (27.0 ml, 13.5 mmol). The suspension was stirred vigorously at 50 C for 48 hours. After removing the THF by rotary evaporation, the aqueous solution was acidified with concentrated HCl to ph < 4. The white precipitation was collected by filtration, washed with deionized water, and dried under vacuum (96% yield). 1 H NMR (400 MHz, DMSO-d 6, δ): 7.87 (s, 3H, Ar H), 7.86 (d, J = 8.2 Hz, 3H, Ar H), 7.35 (s, 3H, Ar H), 7.12 (d, J = 8.4 Hz, 3H, Ar H). 13 C NMR (400 MHz, DMSO-d 6, δ): (C=O), (C-NH 2 ), , , , , , , , ESI (m/z): [M H] calcd for S3

4 C 27 H 20 N 3 O 6, ; found, ATR-FTIR (cm 1 ): 2918 (br), 1672 (s), 1608 (m), 1592 (m), 1512 (w), 1455 (w), 1416 (w), 1380 (m), 1306 (w), 1237 (w), 1165 (s), 1099 (w), 1077 (w), 1036 (w), 961 (w), 895 (w), 860 (w), 834 (w), 774 (s), 700 (w), 674 (w), 655 (w), 644 (w), 585 (w), 555 (w), 532 (w). Synthesis of Compound 3: A mixture of compound 1 (0.91g, 2.0 mmol) and methyl 2-methoxy-4- bromon-benzoate (1.6 g, 6.5 mmol) was dissolved in 48 ml mixed solvent of p-dioxane/h 2 O (1:1 v/v), which was deoxygenated by three freeze-pump-thaw cycles and protected under N 2 atmosphere. After quickly adding of CsF (2.7 g, 18 mmol) and Pd(dppf)Cl 2 (0.11 g, 0.15 mmol), the suspension was heated and stirred vigorously at 90 C for 24 hours. After cooling down to room temperature, the resulting suspension was added with 200 ml of 20% NH 4 Cl solution, and extracted three times with 70 ml EtOAc using a 250-mL separatory funnel. The organic layers were combined, washed with saturated brine, dried with anhydrous Na 2 SO 4 and filtered. A crude product was obtained after removing all the solvent by rotary evaporation, and further purified by quick chromatography using CH 2 Cl 2 as eluent (54% isolated yield). Synthesis of linker D: Compound 3 (0.77 g, 1.5 mmol) was dissolved in 30 ml THF, added with 0.5 M NaOH aqueous solution (30 ml, 15 mmol). The suspension was stirred vigorously at 50 C for 48 hours. After removing the THF by rotary evaporation, the aqueous solution was acidified with concentrated HCl to ph < 2. The white precipitation was collected by filtration, washed with deionized water, and dried under vacuum (98% yield). 1 H NMR (400 MHz, DMSO-d 6, δ): (s, 3H, COOH), 8.06 (s, 3H, Ar H), 7.79 (d, J = 7.9 Hz, 3H, Ar H), 7.53 (s, 3H, Ar H), 7.51 (d, J = 8.1 Hz, 3H, Ar H), 3.97 (s, 9H, -OMe). 13 C NMR (400 MHz, DMSO-d 6, δ): (COOH), (C-OMe), , , , , , , , (-OCH 3 ). ESI (m/z): [M H] calcd for C 30 H 23 O 9, ; found, ATR-FTIR (cm 1 ): 3257 (m), 2957 (w), 2923 (w), 2854 (w), 1741 (s), 1608 (s), 1565 (m), 1499 (w), 1455 (w), 1437 (m), 1393 (s), 1306 (w), 1281 (w), 1265 (m), 1233 (m), 1205 (m), 1180 (m), 1136 (m), 1102 (w), 1076 (m), 1019 (s), 935 (m), 852 (m), 833 (m), 771 (m), 749 (m), 714 (w), 679 (s), 611 (w), 553 (w), 464 (w). S4

5 Synthesis of Compound 4: A mixture of compound 1 (0.91g, 2.0 mmol) and methyl 2,5-difluoro-4- bromon-benzoate (1.6 g, 6.5 mmol) was dissolved in 48 ml mixed solvent of p-dioxane/h 2 O (1:1 v/v), which was deoxygenated by three freeze-pump-thaw cycles and protected under N 2 atmosphere. After quickly adding of CsF (2.7 g, 18 mmol) and Pd(dppf)Cl 2 (0.11 g, 0.15 mmol), the suspension was heated and stirred vigorously at 90 C for 24 hours. After cooling down to room temperature, the resulting suspension was added with 200 ml of 20% NH 4 Cl solution, and extracted three times with 70 ml EtOAc using a 250-mL separatory funnel. The organic layers were combined, washed with saturated brine, dried with anhydrous Na 2 SO 4 and filtered. A crude product was obtained after removing all the solvent by rotary evaporation, and further purified by quick chromatography using CH 2 Cl 2 /Hexane (8:1 v/v) as eluent (55% isolated yield). Synthesis of linker F: Compound 4 (0.250 g, mmol) was dissolved in 9 ml THF, added with 0.5 M NaOH aqueous solution (9.0 ml, 4.5 mmol). The suspension was stirred vigorously at 50 C for 24 hours. After removing the THF by rotary evaporation, the aqueous solution was acidified with concentrated HCl to ph < 2. The white precipitation was collected by filtration, washed with deionized water, and dried under vacuum (98% yield). 1 H NMR (400 MHz, DMSO-d 6, δ): 8.24 (s, 3H, Ar H), 8.00 (s, 3H, Ar H), 7.98 (s, 3H, Ar H). 13 C NMR (400 MHz, DMSO-d 6, δ): (COOH), (C-F), , , , ESI (m/z): [M H] calcd for C 27 H 11 O 6 F 6, ; found, ATR-FTIR (cm 1 ): 3515 (w), 2921 (m), 2853 (w), 2641 (br), 1738 (s), 1623 (s), 1563 (s), 1497 (w), 1455 (m), 1429 (w), 1390 (s), 1332 (m), 1246 (m), 1227 (m), 1188 (s), 1116 (m), 1074 (w), 1038 (s), 976 (m), 902 (w), 841 (s), 785 (m), 764 (m), 737 (m), 703 (w), 625 (m), 586 (w), 572 (m), 528 (m), 506(w), 432 (w). Synthesis of Compound 6: A mixture of compound 1 (0.91g, 2.0 mmol) and methyl 2-fluoro-4-bromonbenzoate (1.6 g, 6.5 mmol) was dissolved in 48 ml mixed solvent of p-dioxane/h 2 O (1:1 v/v), which was deoxygenated by three freeze-pump-thaw cycles and protected under N 2 atmosphere. After quickly adding of CsF (2.7 g, 18 mmol) and Pd(dppf)Cl 2 (0.11 g, 0.15 mmol), the suspension was heated and stirred vigorously at 90 C for 24 hours. After cooling down to room temperature, the resulting suspension was added with 200 ml of 20% NH 4 Cl solution, and extracted three times with 70 ml EtOAc using a 250-mL separatory funnel. The organic layers were combined, washed with saturated brine, dried with anhydrous Na 2 SO 4 and filtered. A crude S5

6 product was obtained after removing all the solvent by rotary evaporation, and further purified by quick chromatography using CH 2 Cl 2 /Hexane (8:1 v/v) as eluent (55% isolated yield). 1 H NMR (400 MHz, DMSO-d 6, δ): 8.17 (s, 3H, Ar H), 8.05 (d, J = 12.0 Hz, 3H, Ar H), 7.95 (m, 6H, Ar H), 3.90 (s, 9H, -COOCH 3 ). Synthesis of linker H: Compound 6 (0.250 g, mmol) was dissolved in 9 ml THF, added with 0.5 M NaOH aqueous solution (9.0 ml, 4.5 mmol). The suspension was stirred vigorously at 50 C for 24 hours. After removing the THF by rotary evaporation, the aqueous solution was acidified with concentrated HCl to ph < 2. The white precipitation was collected by filtration, washed with deionized water, and dried under vacuum (98% yield). 1 H NMR (400 MHz, DMSO-d 6, δ): 13.31(s, 3H, COOH), 8.17 (s, 3H, Ar H), 8.00 (dd, J =11.9 Hz, 3H, Ar H), 7.95 (d, J = 7.9 Hz, 3H, Ar H), 7.89 (dd, J = 8.2 Hz, 3H Ar H). 13 C NMR (400 MHz, DMSO-d 6, δ): (COOH), , , , , , , (m) , , , ESI (m/z): [M H] calcd for C 27 H 14 F 3 O 6, ; found, ATR-FTIR (cm 1 ): 2920 (w), 2661 (w), 2548 (w), 1692 (s), 1616 (s), 1564 (m), 1506 (w), 1454 (m), 1417 (m), 1394 (m), 1290 (m), 1249 (m), 1205 (m), 1183 (m), 1151 (m), 1101 (m), 1101 (m), 1070 (m), 957 (m), 899 (m), 864 (m), 835 (m), 774 (s), 759 (s), 692 (m), 638 (w), 593 (w), 553 (m), 496 (w), 453 (m), 412 (w). Synthesis of Compound 7: A mixture of compound 1 (0.91g, 2.0 mmol) and methyl 2-methyl-4-bromonbenzoate (1.6 g, 6.5 mmol) was dissolved in 48 ml mixed solvent of p-dioxane/h 2 O (1:1 v/v), which was deoxygenated by three freeze-pump-thaw cycles and protected under N 2 atmosphere. After quickly adding of CsF (2.7 g, 18 mmol) and Pd(dppf)Cl 2 (0.11 g, 0.15 mmol), the suspension was heated and stirred vigorously at 90 C for 24 hours. After cooling down to room temperature, the resulting suspension was added with 200 ml of 20% NH 4 Cl solution, and extracted three times with 70 ml EtOAc using a 250-mL separatory funnel. The organic layers were combined, washed with saturated brine, dried with anhydrous Na 2 SO 4 and filtered. A crude product was obtained after removing all the solvent by rotary evaporation, and further purified by quick chromatography using CH 2 Cl 2 /Hexane (8:1 v/v) as eluent (55% isolated yield). 1 H NMR (400 MHz, CDCl 3, δ): 8.05 (d, J = 8.0 Hz, 3H, Ar H), 7.82 (s, 3H, Ar H), 7.56 (m, 6H, Ar H), 3.93 (s, 9H, -COOCH 3 ), 2.71 (s, 9H, - CH 3 ). S6

7 Synthesis of linker I: Compound 7 (0.250 g, mmol) was dissolved in 9 ml THF, added with 0.5 M NaOH aqueous solution (9.0 ml, 4.5 mmol). The suspension was stirred vigorously at 50 C for 24 hours. After removing the THF by rotary evaporation, the aqueous solution was acidified with concentrated HCl to ph < 2. The white precipitation was collected by filtration, washed with deionized water, and dried under vacuum (97% yield). 1 H NMR (400 MHz, DMSO-d 6, δ): (s, 1H, COOH), 8.03(s, 3H, Ar H), 7.96 (d, J = 8.3 Hz, 3H, Ar H), 7.85 (s, 3H, Ar H), 7.81 (d, J = 8.2 Hz, 3H, Ar), 2.65 (s, 9H, CH 3 ). 13 C NMR (400 MHz, DMSO-d 6, δ): (COOH), , , , , , , , , 21.47(CH 3 ). [M H] calcd for C 30 H 23 O 6, ; found, ATR-FTIR (cm 1 ): 3257 (m), 2957 (w), 2923 (w), 2854 (w), 1741 (s), 1608 (s), 1565 (m), 1499 (w), 1455 (w), 1437 (m), 1393 (s), 1306 (w), 1281 (w), 1265 (m), 1233 (m), 1205 (m), 1180 (m), 1136 (m), 1102 (w), 1076 (m), 1019 (s), 935 (m), 852 (w), 833 (m), 771 (m), 749 (m), 714 (w), 679 (s), 611 (w), 553 (w), 464 (w). S7

8 COOMe COOMe I 1 + NO 2 Pd(AcO)2/(Bu)4 NBr/K 3 PO 4 THF NO 2 NO 2 Fe powder AcOH NH 2 NH 2 COOMe MeOOC O 2 N COOMe MeOOC H 2 N COOMe 8 9 (46% yield) (97% yield) Scheme S2. Synthesis of the ester form of 1,3,5-tris(2 -amino-4 -carboxyphenyl)benzene. Synthesis of Compound 8: A mixture of methyl-4-iodo-3-nitrobenzoate (10 g, 33 mmol), Pd(AcO) 2 (75 mg, 0.22 mmol), (Bu) 4 NBr (125 mg), and K 3 PO 4 (13.5 g) in THF (300 ml) was added to 1 (5.0 g, 11 mmol). The mixture was refluxed at 70 C for 48 h under argon atmosphere. The solution was filtered through Celite and the filtered solution was evaporated. Purification of the crude product by flash column chromatography on silica gel (fourth spot, hexane:etoac = 3:2, R f = 0.35) provided pale yellow powders (3.0 g, 46% yield). 1 H NMR (DMSO-d 6, 400 MHz, δ): 8.51 (s, 3H), 8.30 (d, 3H, J = 8.0 Hz), 7.78 (d, 3H, J = 8.0Hz), 7.58 (s, 3H), 3.94 (s, 9H). 13 C NMR (DMSO-d 6, 400 MHz, δ): 164.8, 148.8, 138.7, 137.8, 133.7, 133.6, 130.9, 128.0, 125.5, FT-IR (KBr, cm 1 ) 3488 (br), 3086 (w), 2955 (w), 2850 (w), 1729 (vs), 1619 (m), 1534 (vs), 1437 (m), 1355 (m), 1289 (s), 1260 (m), 1194 (w), 1152 (w), 1119 (m), 980 (w), 905 (w), 855 (w), 824 (w), 813 (w), 759 (m), 708 (w), 416(w). Synthesis of Compound 9: A solution of 8 (2.7 g, 4.3 mmol) in acetic acid (100 ml) was added to Fe powder (3.6 g, 65 mmol). The mixture was stirred at room temperature for 20 h under argon atmosphere. The solution was filtered through Celite and the filtered solution was evaporated. The residue was dissolved in EtOAc and H 2 O. The organic layer was washed with a saturated NaHCO 3 (aq.) and brine, dried over MgSO 4, and filtered. The solvent was removed by rotary evaporation, yielding ivory powders (2.2 g, 97% yield). 1 H- NMR (DMSO-d 6, 400 MHz, δ): 7.48 (s, 3H), 7.43 (s, 3H), 7.25 (d, 3H, J = 8.0 Hz), 7.21 (d, 3H, J = 8.0Hz), 5.33 (s, 6H), 3.83 (s, 9H). 13 C NMR (DMSO-d 6, 400 MHz, δ): FT-IR (KBr, cm -1 ): 3450 (m), 3427 (m), 3371 (m), 3001(w), 2951 (w), 2848 (w), 1718 (vs), S8

9 1626 (m), 1591 (w), 1571 (w), 1508 (w), 1439 (m), 1403 (w), 1298 (s), 1248 (m), 1226 (m), 1147 (w), 1113 (m), 1060 (w), 996 (w), 892(w), 866 (w), 763(m), 412 (w). Synthesis of linker J: A solution of 9 (4.0 g, 7.6 mmol) in a mixture of aqueous LiOH H 2 O (0.6 M, 120 ml), THF (120 ml), and MeOH (60 ml) was stirred at room temperature for 20 h. After evaporation, the residue was acidified with 1M HCl (< 72 ml). The precipitate was filtered, washed with H 2 O, and dried under vacuum to give ivory solids. 1 H NMR (400 MHz, DMSO-d 6, δ): (s, 3H, COOH), 7.47 (s, 3H, Ar H), 7.40 (s, 3H, Ar H), 7.21 (m, 6H, Ar H), 5.26 (s, 6H, -NH 2 ). 13 C NMR (400 MHz, DMSO-d 6, δ): (COOH), , , , , , , , ESI: [M H] calcd for C 27 H 20 N 3 O 6, ; found, ATR-FTIR (cm 1 ):3408 (w), 3363 (w), 3329 (w), 3296 (w), 2736 (br), 2614 (br), 1707 (m), 1634 (m), 1584 (m), 1532 (w), 1502 (w), 1444 (m), 1396 (m), 1333 (m), 1301 (m), 1254 (w), 1226 (m), 1198 (s), 1122 (m), 1083 (m), 1057 (w), 997 (w),967 (m), 943 (w), 919 (m), 901 (m), 885 (m), 849 (w), 800 (m), 766 (s), 742 (s), 729 (m), 715 (m), 677 (m), 653 (m), 630 (m), 563 (m), 502 (w), 471 (m). S9

10 COOMe COOMe Br I a Br + B O O b COOMe Br Br COOMe 10 (43% yield) B O O Br (40% yield) c MeOOC COOMe NH 2 COOMe B O O NH 2 (98% yield) d MeOOC COOMe Scheme S3. Syntheses of the ester form of a heterofunctionalized BTB derivative based on multiple steps of Suzuki-Miyaura cross-coupling reaction. Synthesis of compound 10: p-dioxane/h 2 O solution (18 ml, 8:1 v:v) was purged with N 2 and then transferred via a cannula into a three-neck round bottomed flask which was charged with a (510 mg, 1.62 mmol) and b (339 mg, 1.29 mmol). CsF (588 mg, 3.87 mmol) and PdCl 2 (dppf) (23.4 mg, mmol) were then quickly added into the flask. The resulting mixture was stirred vigorously and heated at 90 C for 24 hours. After cooling down to room temperature, 250 ml of 20% NH 4 Cl solution was added into the mixture. The product was extracted by using 70 ml EtOAc three times. The organic layers were combined, washed with saturated brine, and dried with anhydrous MgSO 4. After filtration, the solvent was removed, and the crude product was further purified by quick chromatography using CH 2 Cl 2 as eluent (43% yield). 1 H NMR (400 MHz, DMSO-d 6, δ): 8.03 (d, J = 8.7 Hz, 2H, Ar H), 7.98 (d, J = 1.7 Hz, 2H, Ar H), 7.90 (m, 3H, Ar H), 3.88 (s, 3H, -COOCH 3 ). Synthesis of compound 11: p-dioxane/h 2 O solution (18 ml, v:v = 8:1) was purged with N 2 and then transferred via a cannula into a three-neck round bottomed flask which was charged with 10 (402 mg, 1.08 S10

11 mmol) and c (293 mg, mmol). CsF (428 mg, 2.88 mmol) and PdCl 2 (dppf) (17.0 mg, mmol) were then quickly added into the flask. The resulting mixture was stirred vigorously and heated at 90 C for 24 hours. After cooling down to room temperature, 150 ml of 20% NH 4 Cl solution was added into the mixture. The product was extracted by using 40 ml EtOAc three times. The organic layers were combined, washed with saturated brine, and dried with anhydrous MgSO 4. After filtration, the solvent was removed, and the crude product was further purified by quick chromatography using CH 2 Cl 2 /EtOAc (12:1 v/v) as eluent (40% yield). 1 H NMR (400 MHz, DMSO-d 6, δ): 8.83 (d, J = 8.8 Hz, 1H, Ar H), 8.19 (d, J = 7.8 Hz, 1H, Ar H), 8.10 (t, 1H, Ar H), 8.04 (d, J = 8.6 Hz, 2H, Ar H), 7.96 (d, J = 8.6 Hz, 2H, Ar H), 7.88 (d, J = 8.1 Hz, Ar H), 7.85 (t, 1H, Ar H), 7.75 (t, 1H, Ar H), 7.71 (m, 1H, Ar H), 7.63 (m, 2H, Ar H), 3.98 (s, 3H, -COOCH 3 ), 3.88 (s, 3H, - COOCH 3 ). Synthesis of compound 12: p-dioxane/h 2 O solution (9 ml, 8:1 v:v) was purged with N 2 and then transferred via a cannula into a three-neck round bottomed flask which was charged with 11 (200 mg, 0.42 mmol) and d (212 mg, mmol). CsF (190 mg, 1.26 mmol) and PdCl 2 (dppf) (15.24 mg, mmol) were then quickly added into the flask. The resulting mixture was stirred vigorously and heated at 90 C for 24 hours. After cooling down to room temperature, 80 ml of 20% NH 4 Cl solution was added into the mixture. The product was extracted by using 30 ml EtOAc three times. The organic layers were combined, washed with saturated brine, and dried with anhydrous MgSO 4. After filtration, the solvent was removed, and the crude product was further purified by quick chromatography using 2:1 Hexane/EtOAc as eluent (96% yield). 1 H NMR (400 MHz, DMSO-d 6, δ): 8.87 (d, J = 9.0 Hz, 1H, Ar H), 8.23 (d, J = 7.5 Hz, 1H, Ar H), 8.10 (t, 1H, Ar H), 8.08 (d, J = 8.6 Hz, 2H), 8.03 (d, J = 8.7 Hz, 2H), 7.97 (d, J = 8.1 Hz, 1H, Ar H), 7.88 (t, 1H, Ar H), 7.81 (d, J = 8.5 Hz, 1H, Ar H), 7.77 (t, 1H, Ar H), 7.75~7.61 (m, 4H, Ar H), 7.28 (s, 1H, Ar H), 7.07 (d, J = 8.7 Hz, 1H, Ar H), 6.71 (s, 2H, -NH 2 ), 3.99 (s, 3H, -COOCH 3 ), 3.89 (s, 3H, -COOCH 3 ), 3.82 (s, 3H, -COOCH 3 ). Synthesis of linker K: A NaOH aqueous solution (9.00 ml, 4.56 mmol) was added into 9 ml THF solution of 12 in (226 mg, mmol). Then the mixture was stirred vigorously at 65 C for 24 hours. After cooling down to room temperature, the THF was removed by rotary evaporation, and the aqueous solution was S11

12 acidified with concentrated HCl to ph < 2. The white precipitation was collected by filtration, washed with deionized water, and dried under vacuum (87% yield). 1 H NMR (400 MHz, DMSO-d 6, δ): (br, 3H, - COOH), 8.51 (d, J = 8.8 Hz, 1H, Ar H), 7.70 (d, J = 7.7 Hz, 1H, Ar H), 7.62~7.35 (m, 6H, Ar H), 7.31 (s, 1H, Ar H), 7.25 (d, J = 8.3 Hz, 1H, Ar H), 7.19 (s, 1H, Ar H), 7.14 (t, J = 5.9 Hz, 2H, Ar H), 7.06~7.00 (m, 1H, Ar H), 6.64 (s, 1H, Ar H), 6.43 (d, J = 8.6 Hz, 1H, Ar H). 13 C NMR (400 MHz, DMSO-d 6, δ): (COOH), (COOH), (COOH), , , , , , , , , , , , , , , , , , , , , ESI (m/z): [M H] calcd for C 31 H 20 NO 6, ; found, ATR-FTIR (cm 1 ): 3487 (w), 3368 (w), 2923 (w), 2633 (vw), 2536 (w), 1678 (s), 1609 (m), 1591 (m), 1548 (m), 1514 (m), 1450 (w), 1412 (m), 1381 (m), 1282 (m), 1234 (s), 1143 (w), 1106 (m), 1016 (w), 964 (w), 892 (w), 851 (m), 772 (s), 704 (m), 667 (w), 643 (w), 573 (w), 537 (w), 463 (w), 443 (w). Characterization of linker C: 1 H NMR (400 MHz, DMSO-d 6, δ): 8.61 (s, 3H, Ar H), 8.41 (d, J = 7.6 Hz, 3H, Ar H), 8.33 (s, 3H, Ar H), 8.02 (d, J = 8.1 Hz, 3H, Ar H). 13 C NMR (400 MHz, DMSO-d 6, δ): (COOH), , , , , , , , ESI (m/z): [M H] calcd for C 27 H 14 N 3 O 12, ; found, ATR-FTIR (cm 1 ): 3504 (br), 3080 (br), 1686 (m), 1614 (m), 1560 (w), 1528 (s), 1502 (m), 1450 (w), 1398 (m), 1353 (s), 1227 (s), 1146 (m), 1110 (w), 1057 (m), 977 (w), 927 (w), 908 (w), 881 (m), 845 (m), 820 (m), 771 (m), 748 (m), 693 (m), 645 (m), 579 (m), 522 (w), 484 (w), 466 (w), 452 (w), 432 (w). Characterization of linker E: 1 H NMR (400 MHz, DMSO-d 6, δ): 7.97 (s, 3H, Ar H), 7.81 (d, J = 7.8 Hz, 3H, Ar H), 7.61 (s, 3H, Ar H), 7.57 (d, J = 7.3 Hz, 6H, Ar H), 7.50 (d, J = 8.1 Hz, 3H, Ar H), 7.39 (m, 6H, Ar H), 7.31 (m, 6H Ar H), 5.40 (s, 6H). 13 C NMR (400 MHz, DMSO-d 6, δ): (COOH), , , , , , , , , , , ESI: [M H] calcd for C 48 H 35 O 9, ; found, ATR-FTIR (cm 1 ): 3245 (w), 3032 (w), 2974 (w), 1718 (s), 1687 (m), 1604 (s), 1562 (m), 1498 (m), 1447 (m), 1392 (s), 1304 (m), 1262 (m), 1215 (m), 1189 (s), 1138 (m), 1101 (w), 1074 (m), 990 (m), 910 (m), 835 (m), 767 (m), 733 (s), 692 (s), 626 (m), 556 (w), 485 (w), 459 (w). S12

13 Characterization of linker G:. 1 H NMR (400 MHz, DMSO-d 6, δ): (s, 3H, COOH), 8.97 (d, J = 7.8 Hz, 3H, Ar H), 8.22 (d, J = 7.8 Hz, 3H, Ar H), 8.22 (d, J = 7.8 Hz, 3H, Ar H), 7.78 (d, J = 7.8 Hz, 3H, Ar H), 7.75 (s, 1H, Ar H), (m, 2H, Ar H). 13 C NMR (400 MHz, DMSO-d 6, δ): (COOH), , , , , , , , , , , ESI (m/z): [M H] calcd for C 39 H 23 O 6, ; found, ATR-FTIR (cm 1 ): 2920 (w), 2852 (w), 1676 (s), 1574 (m), 1512 (m), 1462 (m), 1421 (m), 1374 (m), 1312 (w), 1282 (m), 1249 (s), 1193 (m), 1165 (m), 1139 (m), 1037 (w), 1037 (w), 958 (w), 891 (m), 849 (m), 794 (m), 773 (s), 718 (m), 658 (w), 642 (m), 606 (w), 544 (w), 5114 (w), 482 (w), 464 (w), 455 (w), 428 (m). S13

14 Section S2. Single-Crystal X-ray Diffraction Analyses MOF-177-B. A crystal of as-synthesized MOF-177-B was sealed in a glass capillary. Diffraction data were collected with a Bruker ApexII CCD detector using Cu Kα (λ = Å) X-ray source. The data were corrected for the absorption using the SADABS routine, no correction was made for extinction or decay. The structure was solved by direct methods using the SHELXTL software package and further developed with difference Fourier syntheses. 3 All non-hydrogen atoms on the framework were refined anisotropically; all hydrogen atoms were generated geometrically and refined in the riding mode. All the phenyl rings are treated with rigid constrains; occupancies of disordering sets were refined using free variables. 4 Highly disordered guest molecules could not be modeled, whose contribution to diffraction was deducted using SQUEEZE routine in the PLATON software package. 5 Figure S1. Asymmetry unit in the single-crystal structure of MOF-177-B (thermal ellipsoids with 10% probability). Hydrogen atoms are omitted for clarity; dashed bonds represent the disordering parts. S14

15 Table S1. Crystal data and structure determination for MOF-177-B Compound MOF-177-B Empirical formula C 108 H 60 N 12 O 26 Zn 8 Formula weight Crystal system Trigonal Space group P3 1c (No. 163) a (Å) (8) b (Å) (8) c (Å) (7) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 35912(2) Z 4 Crystal density (g/cm 3 ) Absorption coefficient (mm -1 ) F(000) 4960 Crystal size (mm) Temperature (K) 296(2) Radiation Cu Kα Wavelength (Å) Theta min/max ( ) 1.4/43.1 Index ranges -32 h 32; -32 k 32; -26 l 26 Total/Unique data /8724 R int Observed data [I > 2σ(I)] 4249 N ref /N par 8724/454 R 1 [I > 2σ(I)] a wr 2 (all data) b S c 0.98 Completeness (%) 100 Largest diff. peak/hole (e/å 3 ) 0.36/-0.39 a R 1 = Σ F o - F c /Σ F o ; b wr 2 = [Σw(F 2 o - F 2 c ) 2 /Σw(F 2 o ) 2 ] 1/2 ; c S = [Σw(F 2 o - F 2 c ) 2 /(N ref - N par )] 1/2. S15

16 MOF-177-D. A crystal of as-synthesized MOF-177-D was sealed in a glass capillary. Diffraction data were collected with a Bruker Apex II CCD detector using Cu Kα (λ = Å) X-ray source. The data were corrected for the absorption using the SADABS routine, no correction was made for extinction or decay. The structure was solved by direct methods using the SHELXTL software package and further developed with difference Fourier syntheses. 3 Non-hydrogen atoms on the framework were refined anisotropically; all hydrogen atoms were generated geometrically and refined in the riding mode. All the phenyl rings are treated with rigid constrains; occupancies of disordering sets were refined using free variables. 4 Highly disordered guest molecules and some of the -OMe groups could not be modeled, whose contribution to diffraction was deducted using SQUEEZE routine in the PLATON software package. 5 Figure S2. Asymmetry unit in the single-crystal structure of MOF-177-D (thermal ellipsoids with 10% probability). Hydrogen atoms are omitted for clarity; dashed bonds represent the disordering parts. S16

17 Table S2. Crystal data and structure determination for MOF-177-D Compound MOF-177-D Empirical formula C H 67.5 O 33.5 Zn 8 Formula weight Crystal system Trigonal Space group P3 1c (No. 163) a (Å) (3) b (Å) (3) c (Å) (7) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 35909(2) Z 4 Crystal density (g/cm 3 ) Absorption coefficient (mm -1 ) F(000) 5074 Crystal size (mm) Temperature (K) 296(2) Radiation Cu Kα Wavelength (Å) Theta min/max ( ) 1.4/37.9 Index ranges -29 h 28; -29 k 29; -22 l 23 Total/Unique data 97082/6337 R int Observed data [I > 2σ(I)] 3672 N ref /N par 6337/539 R 1 [I > 2σ(I)] a wr 2 (all data) b S c 0.99 Completeness (%) 99.9 Largest diff. peak/hole (e/å 3 ) 0.51/-0.31 a R 1 = Σ F o - F c /Σ F o ; b wr 2 = [Σw(F 2 o - F 2 c ) 2 /Σw(F 2 o ) 2 ] 1/2 ; c S = [Σw(F 2 o - F 2 c ) 2 /(N ref - N par )] 1/2. S17

18 MOF-177-E. A crystal of as-synthesized MOF-177-E was sealed in a glass capillary. Diffraction data were collected with a Bruker Apex II CCD detector using Cu Kα (λ = Å) X-ray source. The data were corrected for the absorption using the SADABS routine, no correction was made for extinction or decay. The structure was solved by direct methods using the SHELXTL software package and further developed with difference Fourier syntheses. 3 Except the -OBn group, non-hydrogen atoms on the framework were refined anisotropically; all hydrogen atoms were generated geometrically and refined in the riding mode. All the phenyl rings are treated with rigid constrains; occupancies of disordering sets were refined using free variables. 4 Highly disordered guest molecules and some of the -OBn groups could not be modeled, whose contribution to diffraction was deducted using SQUEEZE routine in the PLATON software package. 5 Figure S3. Asymmetry unit in the single-crystal structure of MOF-177-E (thermal ellipsoids with 10% probability). Hydrogen atoms are omitted for clarity; dashed bonds represent the disordering parts. S18

19 Table S3. Crystal data and structure determination for MOF-177-E Compound MOF-177-E Empirical formula C H O 38 Zn 8 Formula weight Crystal system Trigonal Space group P3 1c (No. 163) a (Å) (8) b (Å) (8) c (Å) (7) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 35868(2) Z 4 Crystal density (g/cm 3 ) Absorption coefficient (mm -1 ) F(000) 6778 Crystal size (mm) Temperature (K) 296(2) Radiation Cu Kα Wavelength (Å) Theta min/max ( ) 1.4/40.5 Index ranges -31 h 30; -31 k 31; -24 l 25 Total/Unique data /7512 R int Observed data [I > 2σ(I)] 4805 N ref /N par 7512/484 R 1 [I > 2σ(I)] a wr 2 (all data) b S c 1.53 Completeness (%) 99.9 Largest diff. peak/hole (e/å 3 ) 0.61/-0.35 a R 1 = Σ F o - F c /Σ F o ; b wr 2 = [Σw(F 2 o - F 2 c ) 2 /Σw(F 2 o ) 2 ] 1/2 ; c S = [Σw(F 2 o - F 2 c ) 2 /(N ref - N par )] 1/2. S19

20 MOF-177-F. A crystal of as-synthesized MOF-177-F was sealed in a glass capillary. Diffraction data were collected with a Bruker Apex II CCD detector using Cu Kα (λ = Å) X-ray source. The data were corrected for the absorption using the SADABS routine, no correction was made for extinction or decay. The structure was solved by direct methods using the SHELXTL software package and further developed with difference Fourier syntheses. 3 All non-hydrogen atoms on the framework were refined anisotropically; all hydrogen atoms were generated geometrically and refined in the riding mode. All the phenyl rings are treated with rigid constrains; occupancies of disordering sets were refined using free variables. 4 Highly disordered guest molecules could not be modeled, whose contribution to diffraction was deducted using SQUEEZE routine in the PLATON software package. 5 Figure S4. Asymmetry unit in the single-crystal structure of MOF-177-F (thermal ellipsoids with 10% probability). Hydrogen atoms are omitted for clarity; dashed bonds represent the disordering parts. S20

21 Table S4. Crystal data and structure determination for MOF-177-F Compound MOF-177-F Empirical formula C 108 H 36 F 24 O 26 Zn 8 Formula weight Crystal system Trigonal Space group P3 1c (No. 163) a (Å) (3) b (Å) (3) c (Å) (3) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 36184(8) Z 4 Crystal density (g/cm 3 ) Absorption coefficient (mm -1 ) F(000) 5392 Crystal size (mm) Temperature (K) 296(2) Radiation Cu Kα Wavelength (Å) Theta min/max ( ) 2.0/ 38.1 Index ranges -29 h 28; -26 k 29; -23 l 23 Total/Unique data 55256/ 6075 R int Observed data [I > 2σ(I)] 3793 N ref /N par 6075/517 R 1 [I > 2σ(I)] a wr 2 (all data) b S c 1.31 Completeness (%) 93.5 Largest diff. peak/hole (e/å 3 ) 0.45/-0.43 a R 1 = Σ F o - F c /Σ F o ; b wr 2 = [Σw(F 2 o - F 2 c ) 2 /Σw(F 2 o ) 2 ] 1/2 ; c S = [Σw(F 2 o - F 2 c ) 2 /(N ref - N par )] 1/2. S21

22 MOF-177-G. A crystal of as-synthesized MOF-177-G was sealed in a glass capillary. Diffraction data were collected with a Bruker Apex II CCD detector using synchrotron light source (λ = Å). The data were corrected for the absorption using the SADABS routine, no correction was made for extinction or decay. The structure was solved by direct methods using the SHELXTL software package and further developed with difference Fourier syntheses. 3 All non-hydrogen atoms on the framework were refined anisotropically; all hydrogen atoms were generated geometrically and refined in the riding mode. All the phenyl rings are treated with rigid constrains; occupancies of disordering sets were refined using free variables. 4 Highly disordered guest molecules could not be modeled, whose contribution to diffraction was deducted using SQUEEZE routine in the PLATON software package. 5 Figure S5. Asymmetry unit in the single-crystal structure of MOF-177-G (thermal ellipsoids with 5% probability). Hydrogen atoms are omitted for clarity; dashed bonds represent the disordering parts. S22

23 Table S5. Crystal data and structure determination for MOF-177-G Compound MOF-177-G Empirical formula C 156 H 60 O 26 Zn 8 Formula weight Crystal system Trigonal Space group P3 1c (No. 163) a (Å) (13) b (Å) (13) c (Å) (11) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 35029(32) Z 4 Crystal density (g/cm 3 ) Absorption coefficient (mm -1 ) F(000) 5776 Crystal size (mm) Temperature (K) 296(2) Radiation Synchrotron Wavelength (Å) Theta min/max ( ) 2.9/18.9 Index ranges -30 h 30; -30 k 30; -25 l 24 Total/Unique data 72223/7152 R int Observed data [I > 2σ(I)] 4778 N ref /N par 7152/648 R 1 [I > 2σ(I)] a wr 2 (all data) b S c 1.31 Completeness (%) 99.4 Largest diff. peak/hole (e/å 3 ) 0.35/-0.40 a R 1 = Σ F o - F c /Σ F o ; b wr 2 = [Σw(F 2 o - F 2 c ) 2 /Σw(F 2 o ) 2 ] 1/2 ; c S = [Σw(F 2 o - F 2 c ) 2 /(N ref - N par )] 1/2. S23

24 MOF-177-H. A crystal of as-synthesized MOF-177-H was sealed in a glass capillary. Diffraction data were collected on a Bruker D8-Venture diffractometer using Cu Kα (λ = Å) X-ray source. The data were corrected for the absorption using the SADABS routine, no correction was made for extinction or decay. The structure was solved by direct methods using the SHELXTL software package and further developed with difference Fourier syntheses. 3 All non-hydrogen atoms on the framework were refined anisotropically; all hydrogen atoms were generated geometrically and refined in the riding mode. All the phenyl rings are treated with rigid constrains; occupancies of disordering sets were refined using free variables. 4 Highly disordered guest molecules could not be modeled, whose contribution to diffraction was deducted using SQUEEZE routine in the PLATON software package. 5 Figure S6. Asymmetry unit in the single-crystal structure of MOF-177-H (thermal ellipsoids with 10% probability). Hydrogen atoms are omitted for clarity; dashed bonds represent the disordering parts. S24

25 Table S6. Crystal data and structure determination for MOF-177-H Compound MOF-177-H Empirical formula C 108 H 36 O 26 F 6 Zn 8 Formula weight Crystal system Trigonal Space group P3 1c (No. 163) a (Å) (19) b (Å) (19) c (Å) (17) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 35879(5) Z 4 Crystal density (g/cm 3 ) Absorption coefficient (mm -1 ) F(000) 4744 Crystal size (mm) Temperature (K) 298(2) Radiation Cu Kα Wavelength (Å) Theta min/max ( ) 2.4/40.0 Index ranges -23 h 22; -10 k 30; -16 l 25 Total/Unique data 34015/7258 R int Observed data [I > 2σ(I)] 5125 N ref /N par 7258/499 R 1 [I > 2σ(I)] a wr 2 (all data) b S c 1.13 Completeness (%) 99.7 Largest diff. peak/hole (e/å 3 ) 0.36/-0.28 a R 1 = Σ F o - F c /Σ F o ; b wr 2 = [Σw(F 2 o - F 2 c ) 2 /Σw(F 2 o ) 2 ] 1/2 ; c S = [Σw(F 2 o - F 2 c ) 2 /(N ref - N par )] 1/2. S25

26 MOF-177-I. A crystal of as-synthesized MOF-177-I was sealed in a glass capillary. Diffraction data were collected on a Bruker D8-Venture diffractometer using Cu Kα (λ = Å) X-ray source. The data were corrected for the absorption using the SADABS routine, no correction was made for extinction or decay. The structure was solved by direct methods using the SHELXTL software package and further developed with difference Fourier syntheses. 3 All non-hydrogen atoms on the framework were refined anisotropically; all hydrogen atoms were generated geometrically and refined in the riding mode. All the phenyl rings are treated with rigid constrains; occupancies of disordering sets were refined using free variables. 4 Highly disordered guest molecules could not be modeled, whose contribution to diffraction was deducted using SQUEEZE routine in the PLATON software package. 5 Figure S7. Asymmetry unit in the single-crystal structure of MOF-177-I (thermal ellipsoids with 10% probability). Hydrogen atoms are omitted for clarity; dashed bonds represent the disordering parts. S26

27 Table S7. Crystal data and structure determination for MOF-177-I Compound MOF-177-I Empirical formula C 114 H 54 O 26 Zn 8 Formula weight Crystal system Trigonal Space group P3 1c (No. 163) a (Å) (13) b (Å) (13) c (Å) (11) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 35762(3) Z 4 Crystal density (g/cm 3 ) Absorption coefficient (mm -1 ) F(000) 4744 Crystal size (mm) Temperature (K) 298(2) Radiation Cu Kα Wavelength (Å) Theta min/max ( ) 2.0/50.5 Index ranges -37 h 37; -37 k 37; -14 l 25 Total/Unique data /11920 R int Observed data [I > 2σ(I)] 7566 N ref /N par 11920/515 R 1 [I > 2σ(I)] a wr 2 (all data) b S c 1.26 Completeness (%) 95.0 Largest diff. peak/hole (e/å 3 ) 0.49/-0.50 a R 1 = Σ F o - F c /Σ F o ; b wr 2 = [Σw(F 2 o - F 2 c ) 2 /Σw(F 2 o ) 2 ] 1/2 ; c S = [Σw(F 2 o - F 2 c ) 2 /(N ref - N par )] 1/2. S27

28 MOF-177-J. A crystal of as-synthesized MOF-177-J was sealed in a glass capillary. Diffraction data were collected using a synchrotron light source (λ = Å; Pohang Accelerator Laboratory). The data were corrected for the absorption using the SADABS routine, no correction was made for extinction or decay. The structure was solved by direct methods using the SHELXTL software package and further developed with difference Fourier syntheses. 3 All non-hydrogen atoms on the framework were refined anisotropically; all hydrogen atoms were generated geometrically and refined in the riding mode. All the phenyl rings are treated with rigid constrains; occupancies of disordering sets were refined using free variables. 4 Highly disordered guest molecules could not be modeled, whose contribution to diffraction was deducted using SQUEEZE routine in the PLATON software package. 5 Figure S8. Asymmetry unit in the single-crystal structure of MOF-177-J (thermal ellipsoids with 10% probability). Hydrogen atoms are omitted for clarity; dashed bonds represent the disordering parts. S28

29 Table S8 Crystal data and structure determination for MOF-177-J Compound MOF-177-J Empirical formula C 108 H 72 N 12 O 26 Zn 8 Formula weight Crystal system Trigonal Space group P3 1c (No. 136) a (Å) (5) b (Å) (5) c (Å) (7) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 35893(15) Z 4 Crystal density (g/cm 3 ) Absorption coefficient (mm -1 ) F(000) 5008 Crystal size (mm) Temperature (K) 223(2) K Radiation Synchrotron Wavelength (Å) Theta min/max ( ) 1.9/26.7 Index ranges 0 h 37; -31 k 0; -30 l 30 Total/Unique data 24614/12535 R int Observed data [I > 2σ(I)] 6990 N ref /N par 12535/734 R 1 [I > 2σ(I)] a wr 2 (all data) b S c 0.90 Completeness (%) 99.9 Largest diff. peak/hole (e/å 3 ) 0.35/-0.28 a R 1 = Σ F o - F c /Σ F o ; b wr 2 = [Σw(F 2 o - F 2 c ) 2 /Σw(F 2 o ) 2 ] 1/2 ; c S = [Σw(F 2 o - F 2 c ) 2 /(N ref - N par )] 1/2. S29

30 MOF-177-K. A crystal of as-synthesized MOF-177-K was sealed in a glass capillary. Diffraction data were collected on a Bruker D8-Venture diffractometer using Cu Kα (λ = Å) X-ray source. The data were corrected for the absorption using the SADABS routine, no correction was made for extinction or decay. The structure was solved by direct methods using the SHELXTL software package and further developed with difference Fourier syntheses. 3 Except the highly disordered NH 2 and C 4 H 4 groups, non-hydrogen atoms on the framework were refined anisotropically; all hydrogen atoms were generated geometrically and refined in the riding mode. All the phenyl rings are treated with rigid constrains; occupancies of disordering sets were refined using free variables. 4 Highly disordered guest molecules could not be modeled, whose contribution to diffraction was deducted using SQUEEZE routine in the PLATON software package. 5 Figure S9. Asymmetry unit in the single-crystal structure of MOF-177-K (thermal ellipsoids with 20% probability). Hydrogen atoms are omitted for clarity; dashed bonds represent the disordering parts. S30

31 Table S9 Crystal data and structure determination for MOF-177-K Compound MOF-177-K Empirical formula C 121 H 64 N 4 O 26 Zn 8 Formula weight Crystal system Trigonal Space group P3 1c (No. 136) a (Å) (4) b (Å) (4) c (Å) (4) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 35725(10) Z 4 Crystal density (g/cm 3 ) Absorption coefficient (mm -1 ) F(000) 5068 Crystal size (mm) Temperature (K) 293(2) K Radiation Cu Kα Wavelength (Å) Theta min/max ( ) 2.4/30.9 Index ranges -24 h 22; -20 k 24; -16 l 19 Total/Unique data 22300/3710 R int Observed data [I > 2σ(I)] 2864 N ref /N par 3710/425 R 1 [I > 2σ(I)] a wr 2 (all data) b S c 1.61 Completeness (%) 99.9 Largest diff. peak/hole (e/å 3 ) 0.39/-0.26 a R 1 = Σ F o - F c /Σ F o ; b wr 2 = [Σw(F 2 o - F 2 c ) 2 /Σw(F 2 o ) 2 ] 1/2 ; c S = [Σw(F 2 o - F 2 c ) 2 /(N ref - N par )] 1/2. S31

32 MTV-MOF-177-AF1. A crystal of as-synthesized MOF-177-J was sealed in a glass capillary. Diffraction data were collected on a Bruker D8-Venture diffractometer using Cu Kα (λ = Å) X-ray source. The data were corrected for the absorption using the SADABS routine, no correction was made for extinction or decay. The structure was solved by direct methods using the SHELXTL software package and further developed with difference Fourier syntheses. 3 All non-hydrogen atoms on the framework were refined anisotropically; all hydrogen atoms were generated geometrically and refined in the riding mode. All the phenyl rings are treated with rigid constrains; occupancies of disordering sets were refined using free variables. 4 Highly disordered guest molecules could not be modeled, whose contribution to diffraction was deducted using SQUEEZE routine in the PLATON software package. 5 Figure S10. Asymmetry unit in the single-crystal structure of MTV-MOF-177-AF1 (thermal ellipsoids with 10% probability). Hydrogen atoms are omitted for clarity; dashed bonds represent the disordering parts; orange bonds represent the unfunctionalized linker set. S32

33 Table S10. Crystal data and structure determination for MTV-MOF-177-AF1 Compound MTV-MOF-177-AF1 Empirical formula C 108 H F 7.60 O 26 Zn 8 Formula weight Crystal system Trigonal Space group P3 1c (No. 136) a (Å) (5) b (Å) (5) c (Å) (5) α ( ) 90 β ( ) 90 γ ( ) 120 V (Å 3 ) 35808(13) Z 4 Crystal density (g/cm 3 ) Absorption coefficient (mm -1 ) F(000) 4863 Crystal size (mm) Temperature (K) 298(2) K Radiation Cu Kα Wavelength (Å) Theta min/max ( ) 2.0/38.1 Index ranges -29 h 29; -29 k 29; -24 l 24 Total/Unique data 95016/ 6432 R int Observed data [I > 2σ(I)] 5666 N ref /N par 6432/554 R 1 [I > 2σ(I)] a wr 2 (all data) b S c 1.05 Completeness (%) 99.6 Largest diff. peak/hole (e/å 3 ) 0.42/-0.29 a R 1 = Σ F o - F c /Σ F o ; b wr 2 = [Σw(F 2 o - F 2 c ) 2 /Σw(F 2 o ) 2 ] 1/2 ; c S = [Σw(F 2 o - F 2 c ) 2 /(N ref - N par )] 1/2. S33

34 MOF-155-F. A crystal of as-synthesized MOF-155-F was sealed in a glass capillary. Diffraction data were collected with a Bruker Apex II CCD detector using Cu Kα (λ = Å) X-ray source. The data were corrected for the absorption using the SADABS routine, no correction was made for extinction or decay. The structure was solved by direct methods using the SHELXTL software package and further developed with difference Fourier syntheses. 3 All non-hydrogen atoms on the framework were refined anisotropically; all hydrogen atoms were generated geometrically and refined in the riding mode. All the phenyl rings are treated with rigid constrains; occupancies of disordering sets were refined using free variables. 4 Highly disordered guest molecules could not be modeled, whose contribution to diffraction was deducted using SQUEEZE routine in the PLATON software package. 5 Figure S11. Asymmetry unit in the single-crystal structure of MOF-155-F (thermal ellipsoids with 30% probability). Hydrogen atoms are omitted for clarity; dashed bonds represent the disordering parts. S34

35 Table S11. Crystal data and structure determination for MOF-155-F Compound MOF-155-F Empirical formula C 54 H 18 F 12 O 13 Zn 4 Formula weight Crystal system Cubic Space group Ia3 (No. 206) a (Å) (7) V (Å 3 ) 17503(2) Z 8 Crystal density (g/cm 3 ) Absorption coefficient (mm -1 ) F(000) 5392 Crystal size (mm) Temperature (K) 296(2) K Radiation Cu Kα Wavelength (Å) Theta min/max ( ) 3.4/64.9 Index ranges -30 h 27; -30 k 27; -30 l 30 Total/Unique data 45218/2480 R int Observed data [I > 2σ(I)] 1886 N ref /N par 2480/150 R 1 [I > 2σ(I)] a wr 2 (all data) b S c 1.36 Completeness (%) 99.5 Largest diff. peak/hole (e/å 3 ) 0.74/-0.36 a R 1 = Σ F o - F c /Σ F o ; b wr 2 = [Σw(F 2 o - F 2 c ) 2 /Σw(F 2 o ) 2 ] 1/2 ; c S = [Σw(F 2 o - F 2 c ) 2 /(N ref - N par )] 1/2. S35

36 MOF-155-J. A crystal of as-synthesized MOF-155-J was sealed in a glass capillary. Diffraction data were collected using the synchrotron light source (λ = Å; Pohang Accelerator Laboratory). The data were corrected for the absorption using the SADABS routine, no correction was made for extinction or decay. The structure was solved by direct methods using the SHELXTL software package and further developed with difference Fourier syntheses. 3 All non-hydrogen atoms on the framework were refined anisotropically; all hydrogen atoms were generated geometrically and refined in the riding mode. All the phenyl rings are treated with rigid constrains; occupancies of disordering sets were refined using free variables. 4 Highly disordered guest molecules could not be modeled, whose contribution to diffraction was deducted using SQUEEZE routine in the PLATON software package. 5 Figure S12. Asymmetry unit in the single-crystal structure of MOF-155-J (thermal ellipsoids with 50% probability). Hydrogen atoms are omitted for clarity; dashed bonds represent the disordering parts. S36

37 Table S12. Crystal data and structure determination for MOF-155-J Compound MOF-155-J Empirical formula C 54 H 36 N 6 O 13 Zn 4 Formula weight Crystal system Cubic Space group Pa3 (No. 205) a (Å) (3) V (Å 3 ) 17350(6) Z 8 Crystal density (g/cm 3 ) Absorption coefficient (mm -1 ) F(000) 5008 Crystal size (mm) Temperature (K) 250(2) K Radiation Synchrotron Wavelength (Å) Theta min/max ( ) 1.7/27.8 Index ranges 0 h 30; 0 k 34; -34 l 34 Total/Unique data 39382/7189 R int Observed data [I > 2σ(I)] 6167 N ref /N par 7189/242 R 1 [I > 2σ(I)] a wr 2 (all data) b S c 1.20 Completeness (%) 99.9 Largest diff. peak/hole (e/å 3 ) 3.05/-2.01 a R 1 = Σ F o - F c /Σ F o ; b wr 2 = [Σw(F 2 o - F 2 c ) 2 /Σw(F 2 o ) 2 ] 1/2 ; c S = [Σw(F 2 o - F 2 c ) 2 /(N ref - N par )] 1/2. S37

38 MOF-156-J. A crystal of as-synthesized MOF-156-J was sealed in a glass capillary. Diffraction data were collected using the synchrotron light source (λ = Å; Pohang Accelerator Laboratory). The data were corrected for the absorption using the SADABS routine, no correction was made for extinction or decay. The structure was solved by direct methods using the SHELXTL software package and further developed with difference Fourier syntheses. 3 All non-hydrogen atoms on the framework were refined anisotropically; all hydrogen atoms were generated geometrically and refined in the riding mode. All the phenyl rings are treated with rigid constrains; occupancies of disordering sets were refined using free variables. 4 Highly disordered guest molecules could not be modeled, whose contribution to diffraction was deducted using SQUEEZE routine in the PLATON software package. 5 Figure S13. Asymmetry unit in the single-crystal structure of MOF-156-J (thermal ellipsoids with 10% probability). Hydrogen atoms are omitted for clarity; dashed bonds represent the disordering parts. S38

39 Table S13. Crystal data and structure determination for MOF-156-J Compound MOF-156-J Empirical formula C 54 H 36 N 6 O 13 Zn 4 Formula weight Crystal system Tetragonal Space group P4 2 /mnm (No. 136) a (Å) (3) c (Å) (3) V (Å 3 ) 10034(3) Z 2 Crystal density (g/cm 3 ) Absorption coefficient (mm -1 ) F(000) 1252 Crystal size (mm) Temperature (K) 223(2) K Radiation Synchrotron Wavelength (Å) Theta min/max ( ) 1.3/26.4 Index ranges 0 h 27; -18 k 19; 0 l 18 Total/Unique data 6814/3770 R int Observed data [I > 2σ(I)] 1752 N ref /N par 3770/160 R 1 [I > 2σ(I)] a wr 2 (all data) b S c 1.66 Completeness (%) 99.9 Largest diff. peak/hole (e/å 3 ) 0.32/-0.35 a R 1 = Σ F o - F c /Σ F o ; b wr 2 = [Σw(F 2 o - F 2 c ) 2 /Σw(F 2 o ) 2 ] 1/2 ; c S = [Σw(F 2 o - F 2 c ) 2 /(N ref - N par )] 1/2. S39

40 Figure S14. The qom net in trigonal P3 1c (No. 136) space group with two secondary building units (SBUs) and three linker representing as octahedra and triangles. SBU 1 (red octahedron) locates at (1/3, 2/3, 3/4); SUB 2 (blue octahedron) locates at (1/6, 5/6, 1/4); linker 1 (yellow) locates at (0, 0, 1/4); linker 2 (orange) locates at (1/3, 2/3, 1/4); linker 3 locates at (0.1111, , ). Linkers 1 and 2 sit on the 3-fold axis to bridge SBU1 into hexagon layer. SBU 2 sits at the void of the hexagon layer, which is connected to adjacent SBU 1 by linker 2. Each linker 2 links to two SBU 1 and one SBU 2. ψ I II III IV O O - R 1 O O ψ - F F ψ O O - ψ O O - φ φ φ φ NH 2 R 1 - O O R 1 O O - - O F O F F F O - - O O O O - - O O O NH 2 H 2 N O O - R 1 = H, NH 2, NO 2 Figure S15. The dihedral angles between the peripheral phenylene to the central benzene (ϕ) and the dihedral angles between the peripheral phenylene and the carboxylate. The linkers are classified into four types according to the positions of the functional groups. S40

41 Table S14. The dihedral angles of the peripheral phenylene to the central benzene (ϕ) and those of the carboxylate to the peripheral phenylene (ψ) measured from single-crystal structures of MOF-177-X. Multiple values with slash are provided for disordering parts. MOF-n 177-A 177-B 177-D 177-E 177-F 177-G 177-H 177-I 177-J 177-K Angle (º) Linker 1 to SBU 1 Linker 2 to SBU1 Linker 3 to SBU 1 to SBU 1 to SBU 2 Average ϕ 46.8 / ψ 30.0 / 78.9; 16.5 / / / / 39.4 NA 30.1 / 40.9 ϕ / / ψ 9.1 / / / / 81.4; 58.3 / / 45.2; 19.0 /84.8 ϕ 47.0 / / / / / ψ 49.6 / 18.3; 42.3 / / 87.7; 36.9 / / 54.6; 68.6 / / 57.8; 77.1 / / 38.4; 30.9 / 85.7 ϕ 35.1 / / / ψ 1.8 / 56.8; 50.8 / / 45.1; 14.4 / / / 47.1; 32.8 / 79.6 NA NA 41.5 / 38.8 NA ϕ / ψ 52.9 / / / / / 43.5; NA 38.6 / 72.4 ϕ / ψ 34.0 / / 87.3; 41.9 / / / 60.5 NA 52.2 / 23.6 ϕ 39.0 / / / / / ψ 65.6 / 3.8; 30.5 / / 3.1; 63.2 / / 27.2; 28.6 / / 78.7; 63.2 / / 87.6; 44.7 / 32.7 ϕ 39.5 / / / / / ψ 35.1 / 72.7; 63.7 / / 78.6; 32.2 / / 75.8; 62.7/ / 64.6; 67.0 / / 29.5; 25.7 / 87.8 ϕ / / / / ψ 30.9 / / 38.5; 61.6 / / 65.1; 25.2 / / 87.5; 62.7 / / 15.3; 38.3 / 69.0 ϕ 43.0 / / / / / ψ 36.8 / 75.2; 80.2 / / 30.9; 73.5 / / 33.2; 34.7 / / 13.3; 32.8 / / 35.3; 31.8 / 81.3 NA NA NA NA S41

42 Energy calculation of free rotation of the linkers. In order to understand in more depth the relationship between the ligand conformations and resulting structural types, we performed molecular mechanics (MM) calculations using universal force-field (UFF) on the selected linkers with varying dihedral angles involving the rotation of carboxylate (ψ) and branching benzene (ϕ) as in Figure S15. As there are six bonds that can be rotated in a linker, a full search for the rotational energy map requires 2 6 = 64 angles as parameters, which is formidable for calculations. Therefore, we considered only one branch and two angles (ϕ, ψ) as parameters. For the calculations on fixed conformations without further geometry optimization, ψ angles were fixed at the optimized value and ϕ was rotated by 360º and vice versa. Before the calculations, the geometry of each linker was fully optimized by UFF MM calculations. In addition, the linker A was considered as a representative model for other linker that do not have functional groups at the meta-positions for calculating the energy profiles with varying ϕ angles. The functionalization at the meta-position on the benzoate imposed more restriction (larger energy barrier, ca. 100 kcal/mol) for the rotation of the branching benzene (smaller energy barrier, ca. 15 kcal/mol) (Figure S16). The calculation provides the dihedral angles of the benzoate to the central benzene as 57.4 imposed by m-nh 2 (J) and 63.2 by -C 4 H 4 (G), which deviated from that of pristine BTB (A), We supposed the difference in energy barriers for free rotation and the default dihedral angles are the main factor for topologies selection of functional linkers. It also notable that J and G have more narrow angle ranges for the rotation of the branch benzene, indicating that the linkers are more rigid than A. The plots imply that, within the stable ranges, both linkers can adopt various ϕ angles while A would tend to avoid vertical orientation of the branch benzene. S42

43 Figure S16. Rotational energy barriers calculated by UFF MM calculations with varying ϕ angles. The green circles indicate the angles with the lowest energies (0 kcal/mol). Due to the almost symmetric nature of the profile, the energy values are almost same at the angles, ϕ, ϕ+180º, -ϕ, and (ϕ+180)º; for example, A will have the lowest values at ϕ = -41.7, 138.3, +41.7, and º. The small yellow circles are the angles observed in the crystal structures of A, J, and G, respectively. The angle ranges represent those having small energies ( 3 kcal/mol) to show the relative freedom of rotation for the branching benzoate groups. Interestingly, the observed dihedral angles in the crystal structures of the linkers for MOFs in Table S14 are relatively well matched to the predicted angles in the profiles (Figure S16). A noticeable point is that the ϕ angles of the J linkers are located in a very narrow range around the angle for the geometry-optimized structure. S43

44 The energy profiles for the angles are shown in Figure S17. Most linkers have less than 10 kcal/mol as the rotational energies in ψ except for G; previous quantum mechanical calculations reported that the rotational barrier of carboxylic acid in benzoic acid is 22.4 kj/mol or 5.3 kcal/mol. 6-8 Although the MM calculations give less accurate energy values than quantum mechanical calculations and our models deal with benzoate, we can assess approximately the preferred angle ranges for -COO groups with regarding 5 kcal/mol as acceptable energy barrier. Figure S17 shows that C, G, and J have significantly wide ranges of high energy barriers. A, B, and F have also the high energy ranges but their energies are not so large. Thus, it is expected that A, B, and F would have more flexible conformations than C, G, and J in terms of the dihedral angle variations. Figure S17. Rotational energy barriers calculated by UFF MM calculations with varying ψ angles. The green circles indicate the angles with the lowest energies (0 kcal/mol). A, F, G, and J show symmetric profiles around ψ = 0 whereas B and C asymmetric profiles due to their mono-substituted functional groups at one of the ortho positions. The energy values range from 0 to 20 kcal/mol for each linker. The green circles indicate the angles where the energy values are 0. The light yellow boxes highlight the areas where the energy values are less than 5 kcal/mol. S44

45 Comparison of linker conformations in different resulting topologies Figure S18. The linker conformations in the pyr structures are compared with those in a qom structure. The yellow triangles are molecular planes defined by three C atoms in the -COO groups. The central benzene groups displayed with green sticks sit on the yellow planes in the qom structure whereas those in the pyr structures are located over the yellow planes with the centroid-to-centroid distances. The centroids of the central benzene rings are marked with small green dots. S45

46 Figure S19. The linker conformation in the rtl structure is compared with that in the qom structure: one of the ordered structures for both MOFs has been selected for simplicity. The central benzene groups displayed with green sticks are in-plane for both structures. A notable difference is the relative orientation in the benzoate groups marked with red arrows. S46

47 Figure S20. The fragments of three different framework types are depicted with stick models and the inorganic SBUs are highlighted as polyhedrons. S47

48 Figure S21. The inorganic SBUs, Zn 4 O(CO 2 ) 6, of the qom, pyr, and rtl structures are compared with that of a pcu structure that is represented as a regular octahedron. It is seen that the SBU of qom net deviates largely from a regular octahedron. The 12 angles involving the central atom and six vertex atoms (<C O C) are all 90 for the psu SBU. The smallest/largest angles for each structure are respectively 80.0/100.0 for qom, 88.2/91.8 for pyr, and 87.5/92.5 for rtl. While both the qom and pyr SBUs do not have any 90 angles, the rtl SBU has eight 90 angles and thus, can be considered as the least distorted octahedron. It is notable that the pyr SBU has only two sets of angles, 88.2 and S48