Supporting information for Eddaoudi et al. (2002) Proc. Natl. Acad. Sci. USA 99 (8), ( /pnas ) Supporting Information

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1 Supporting information for Eddaoudi et al. (2002) Proc. Natl. Acad. Sci. USA 99 (8), ( /pnas ) Supporting Information Table 1. Syntheses of MOF MOFn MOF- 102 Link and Abbreviation Cl O 2 C CO 2 Cl Cl 2 -BDC Chem ical Form ula Space Group; a, b, c (Å); a, ß,?( ); V (Å 3 ); Z Cu2(Cl2-BDC)2(DMF)2.(H 2O)(DMF)3.5 P-1; , , ; , , ; 965.6; 1 MOF- 103 O 2 C CO 2 CB-BDC Zn2(CB-BDC)2(H 2O)2 (H 2O)3(DMF)1.8 P21/n; , , ; 90.00, , 90.00; ; 2 MOF- 104 O 2 C CDC CO 2 Zn2(CDC)2(DMF)2 (DMF)2(ClBz) C2/m; , , ; 90.00, , 90.00; ; 2 MOF- 105 O 2 C NDC CO 2 Zn2(NDC)2(DMF)2 (ClBz) P21/c; 8.130, , ; 90.00, , 90.00; ; 2 MOF- 106 O 2 C BPDC CO 2 Fe2(BPDC)2(DMF)2 (H 2O)0.4(DMF)3.6 C2/c; , , ; 90.00, , 90.00; , 4 MOF- 107 MOF- 108 S O 2 C CO 2 TDC S O 2 C CO 2 TDC Cu2(TDC)2(DEF)2 (H 2O) (DEF)3 P-1; , , ; , , ; ; 4 Cu2(TDC)2(CH 3OH)2 (DBF)2 P21/c; , , ; 90.00, , 90.00; , 4 MOF- 109 O 2 C O KDB CO 2 Cu2(KDB)2(DMF)2.(H 2O)2(DMF)8 P21/c; , , ; 90.00, , 90.00; ; 4 MOF- 110 S O 2 C CO 2 TDC Cu2(TDC)2(DMF)2 (H 2O) (DMF)3.5 R(-3)m; , , ; 90.00, 90.00, ; ; 4.5 MOF- 111 MOF- 112 O 2 C CO 2 O 2 C Br Br-BDC CO 2 Br o -Br-m -BDC Cu2(TDC)2(DMF)2 (H 2O)(DMF)2 C2/c; , , ; 90.00, , 90.00; 4127; 4 Cu2(Br-BDC)2(DMF)2 (H 2O)2 (DMF)2 C2/c; , , ; 90.00, , 90.00; ; 12 1

2 Syntheses of MOF (MOF-102): Cu 2 (Cl 2 -BDC) 2 (DMF) 2 (H 2 O) 2 (DMF) 3.5. An exact amount of 2,5- dichlorobenzene dicarboxylic acid, (Cl 2 -BDCH 2 ) (11.20 mg, mmol), and copper(ii) nitrate hemipentahydrate, Cu(NO 3 ) 2 2.5H 2 O, (9.6 mg, mmol) was dissolved in N,N -dimethylformamide (DMF)/ethanol (1.5 ml/0.5 ml). The solution was placed in a Pyrex tube (10 mm 8 mm o.d. i.d., 140 mm length). The evacuated tube was sealed and heated to 80 C for 20 h at a rate of 2.0 C/min, then cooled to room temperature at a rate of 1.0 C/min. The resultant blue crystals was filtered, and washed with the DMF/ethanol mixture (3 5 ml) to yield MOF-102. Elemental analysis: C 32.5 H 46.5 O 15.5 N 5.5 Cl 4 Cu 2 = Cu 2 (Cl 2 -BDC) 2 (DMF) 2 (H 2 O) 2 (DMF) 3.5 : Calcd. C, 37.86; H, 4.55; N, Found C, 37.99; H, 4.07; N, FT-IR: (KBr, cm 1 ): 3440 (br), 2931 (w), 1642 (s), 1580 (w), 1388 (vs), 1327 (w), 1255 (w), 1154 (w), 1108 (w), 1087 (m), 1123 (w), 914 (w), 838 (w), 798 (w), 675 (w), 598 (w). (MOF-103): Zn 2 (CB-BDC) 2 (H 2 O) 2 (H 2 O) 3 (DMF) 1.8. A mixture of anhydrous ZnCl 2 (0.06 g, 0.44 mmol) and 1,2-dihydrocyclobutabenzene-3,6-dicarboxylic acid (CB- BDCH 2 ) (0.05 g, mmol) was dissolved in N,N'-dimethylformamide (10 ml) and transferred to a 20-ml glass vial. An aqueous solution of methylamine (0.6 M) was added dropwise to the solution (2.0 ml). The solution immediately became slightly cloudy. The mixture was vigorously shaken and then allowed to stand at room temperature for several days. Clear rectangular crystals were formed on the bottom of the vial and were collected for analysis by vacuum filtration. Elemental Analysis: C 26 H 36.4 N 1.8 Zn 2 = Zn 2 (CB-BDC) 2 (H 2 O) 2 (H 2 O) 3 (DMF) 1.8 : Calcd. C, 41.64; H, 4.76; N, Found C, 42.89; H, 6.75; N,

3 FT-IR: (KBr cm 1 ): (br), (m), (m), (m), (vs), (s), (vs), (vs), (s), (w), (m), (m), (w), (w), (w), (s), (s), (m), (m), (s). (MOF-104): Zn 2 (CDC) 2 (DMF) 2 (DMF) 2 (ClBz). 1,4-Cubanedicarboxylic acid (CDCH 2 ) (0.420 g, 2.19 mmol) and zinc(ii) nitrate hexahydrate (0.660 g, 2.22 mmol) were dissolved in N,N'-dimethylformamide (30 ml). The solution was then diluted with chlorobenzene (ClBz) (30 ml). The resulting clear solution was distributed equally into six vials. These vials were placed in a larger container having a small vial containing triethylamine (0.50 ml) and chlorobenzene (5 ml), which was sealed and left undisturbed at room temperature. After 12 days, the colorless block-shaped crystals were collected, washed with 3 10 ml of mixed solvent (DMF : ClBz = 1: 1). (MOF-105): Zn 2 (NDC) 2 (DMF) 2 (ClBz). In a 20-ml vial, 2,6-naphtalenedicarboxylic acid (NDCH 2 ) (0.076g, 0.36mmol) and zinc(ii) nitrate hexahydrate (0.110 g, 0.37 mmol) were added along with 5 ml of dimethylformamide (DMF) and 5 ml chlorobenzene (ClBz) an stirred and reactants dissolved. The vial was introduced into a 60-ml vial containing 2 ml of dimethylformamide, 2 ml of chlorobenzene, and 0.15 ml of triethylamine, and then sealed. The mixture was left to crystallize for 3 days and it was then filtered, washed with 3 10 ml of dimethylformamide, and left to air dry yielding g (0.92 %) of MOF-105. Elemental analysis: C 36 H 31 N 2 O 10 ClZn 2 = Zn 2 (NDC) 2 (DMF) 2 (ClBz): Calcd. C, 52.87; H, 3.82; N, 3.43; Cl, Found C, 52.25; H, 3.76; N, 3.36; Cl, FT-IR: (KBr, cm 1 ): 3441 (br), 3092 (w), 3059 (w), 3000 (w), 2960 (w), 2921 (w), 2809 (w), 1835 (w), 1644 (s), 1493 (vs), 1407 (vs), 1361 (s), 1256 (vs), 1190 (w), 1124 (w), 1085 (w), 1019 (w), 927 (w), 874 (w), 841 (w), 788 (s),, 690 (m), 644 (w), 591 (w), 565 (w), 486 (m). 3

4 (MOF-106): Fe 2 (BPDC) 2 (DMF) 2 (H 2 O) 0.4 (DMF) 3.6. Equimolar amounts of iron(ii) bromide, FeBr 2, (0.2 g, mmol) and 4,4-biphenyldicarboxylic acid, BPDCH 2, (0.225 g, mmol) were stirred in 60 ml of N,N'-dimethylformamide at room temperature for 2 h to give an orange solution with partially dissolved BPDC starting material. A mixture of approximately 70% DMF reaction solution and 30% 1-propanol were placed in a 10- mm (OD) Pyrex tube to be evacuated and flame sealed. The reaction tube was heated to 120ºC at a rate of 5ºC/min and held at that temperature for 20 h, then cooled at a rate of 1ºC/min to room temperature. Upon heating, the remaining undissolved starting material goes into solution and crystal formation occurs during the isotherm. The resulting product can be described as a mixture of large, transparent, yellow crystalline plates and a fine red/brown crystalline material in a clear solution. The tube contents are washed with a 3 10 ml DMF/1-propanol (10:3) solution, upon which the larger yellow crystals and fine crystalline powder is isolated and air-dried to give g (61% yield) of MOF-106. Elemental analysis: C 37 H 49 N 3 O 17 Fe 2 = Fe 2 (BPDC) 2 (DMF) 2 (DMF)(H 2 O) 6 : Calcd. C, 48.33: H, 5.37; N, Found C, 47.82; H, 4.49; N, FT-IR: (KBr, cm 1 ): 3064 (w), 2965 (w), 2925 (w), 1673 (s), 1608 (s), 1581 (s), 1529 (s), 1397 (vs, broad), 1299 (vs), 1182 (m), 1104 (m), 1010 (m), 852 (m), 797 (m), 768 (s), 700, (m), 680 (m), 467 (m). (MOF-107): Cu 2 (TDC) 2 (DEF) 2 (H 2 O)(DEF) 3. An exact amount of 2,5- thiophenedicarboxylic acid, (TDCH 2 ) (18.0 mg, mmol), and copper(ii) nitrate hemipentahydrate, Cu(NO 3 ) 2 2.5H 2 O, (23.5 mg, mmol) was dissolved in N,N'- diethylformamide (DEF)/ethanol (1.6 ml/0.4 ml). The solution was placed in a Pyrex tube (10 mm 8 mm o.d. i.d., 140 mm length). The evacuated tube was sealed and heated to 80 C for 20 h at a rate of 2.0 C/min, then cooled to room temperature at a rate of 1.0 C/min. The resultant blue crystals was filtered, and washed with the DEF/ethanol mixture (3 5 ml) to yield MOF

5 Elemental analysis: C 39 H 69 O 16 N 5 S 2 Cu 2 = Cu 2 (TDC) 2 (DEF) 2 (H 2 O)(DEF) 3 : Calcd. C, 44.64; H, 5.99; N, Found C, 44.64; H, 5.99; N, FT-IR: (KBr, cm 1 ): 3430 (br), 2982 (m), 2935 (w), 2875 (w), 1658 (s), 1617 (vs), 1541 (m), 1464 (w), 1383 (vs), 1266(w), 1210 (w), 1123 (w), 1026 (w), 950 (w), 848 (w), 812 (w), 767 (s), 695 (w), 65 (w), 537(w). (MOF-108): Cu 2 (TDC) 2 (CH 3 OH) 2 (DBF). An exact amount of 2,5- thiophenedicarboxylic acid, (TDCH 2 ) (16.8 mg, mmol), and copper(ii) nitrate hemipentahydrate, Cu(NO 3 ) 2 2.5H 2 O, (22.8 mg, mmol) was dissolved in dibutylformamide (DBF)/methanol (0.6 ml/0.3 ml). The solution was placed in a Pyrex tube (10 mm 8 mm o.d. i.d., 140 mm length). The evacuated tube was sealed and heated to 80 C for 20 h at a rate of 2.0 C/min, then cooled to room temperature at a rate of 1.0 C/min. The resultant crystals was filtered, and washed with the DMF/ethanol mixture (3 5ml) to yield MOF-108. Elemental analysis: C 24 H 34 O 13 N 4 S 2 Cu 2 = Cu 2 (TDC) 2 (CH 3 OH) 2 (CH 3 OH) 2 (DMF) 4 : Calcd. C, 37.88; H, 5.45; N, Found C, 37.43; H, 4.96; N, FT-IR: (KBr, cm 1 ): 3440 (br), 2956 (w), 2870 (w), 1617 (s), 1534 (m), 1464 (w), 1378 (vs), 1215(w), 1123 (w), 1026 (w), 848 (w), 772 (m), 537(w). (MOF-109): Cu 2 (KDB) 2 (DMF) 2 (H 2 O) 2 (DMF) 8. An exact amount of benzophenone 4,4'-dicarboxylic acid, KDBH 2, (22.00 mg, mmol) and copper(ii) nitrate hemipentahydrate, Cu(NO 3 ) 2 2.5H 2 O, (19.2 mg, mmol) was dissolved in a 1.5-ml DMF solution. Ethanol (0.5 ml) was added and the solution placed in a Pyrex tube (10 mm 8 mm o.d. i.d., 140 mm length). The evacuated tube was sealed and heated to 80 C for 20 h at a rate of 2.0 C/min, then cooled to room temperature at a rate of 1.0 C/min. The resultant blue crystals was filtered, and washed with the DMF/ethanol mixture (3 5 ml) to yield MOF

6 Elemental analysis: C 60 H 90 O 22 N 10 Cu 2 = Cu 2 (KDB) 2 (DMF) 2 (H 2 O) 2 (DMF) 8 Calcd. C, 50.38; H, 6.34; N, Found C, 50.13; H, 6.24; N, FT-IR: (KBr, cm 1 ): 3429 (br), 2935 (m), 1668 (s), 1617 (s), 1556(m), 1510(m), 1408 (vs), 1301 (w), 1271 (m), 1113 (w), 1021 (w), 940 (m), 843 (m), 787 (m), 731 (m), 537 (w), 450(w). (MOF-110): Cu 2 (TDC) 2 (DMF) 2 (H 2 O)(DMF) 2. An exact amount of 2,5- thiophenedicarboxylic acid, (TDCH 2 ) (18.0 mg, mmol), and copper(ii) nitrate hemi-pentahydrate, Cu(NO 3 ) 2 2.5H 2 O, (23.5 mg, mmol) was dissolved in DMF/ethanol (1.5ml/0.5 ml). The solution was placed in a Pyrex tube (10 mm 8 mm o.d. i.d., 140 mm length). The evacuated tube was sealed and heated to 80 C for 20 h at a rate of 2.0 C/min, then cooled to room temperature at a rate of 1.0 C/min. The resultant green, polyhedron crystals was filtered, and washed with the DMF/ethanol mixture (3 5 ml) to yield MOF-110. Elemental analysis: C 24 H 34 O 13 N 4 S 2 Cu 2 = Cu 2 (TDC) 2 (DMF) 2 (H 2 O)(DMF) 2 : Calcd. C, 37.06; H, 4.41; N, Found C, 37.26; H, 4.50; N, FT-IR: (KBr, cm 1 ): 3440 (br), 3109 (w), 2930 (w), 1668 (s), 1612 (vs), 1536 (m), 1378 (vs), 1255(w), 1103 (w), 1062 (w), 1031 (w), 863 (w), 812 (w), 777 (m), 680 (w), 537(w). (MOF-111): Cu 2 (Br-BDC) 2 (DMF) 2 (DMF) 3 (H 2 O) 2. An exact amount of 2- bromobenzenedicaroxylic acid (Br-BDCH 2 ) (17.25 mg, 0.07 mmol), and copper(ii) nitrate hemipentahydrate, Cu(NO 3 ) 2 2.5H 2 O, (16.13 mg, 0.07 mmol) was dissolved in solvent mixture DMF/ethanol (1.5 ml/0.5 ml). The solution was placed in a Pyrex tube (10 mm 8 mm o.d. i.d., 140 mm length). The evacuated tube was sealed and heated to 80 C for 20 h at a rate of 2.0 C/min, then cooled to room temperature at a rate of 1.0 C/min. The resultant blue crystals was filtered, and washed with the DMF/ethanol mixture (3 5 ml) to yield MOF

7 Elemental analysis: C 31 H 25 Br 2 O 15 N 5 Cu 2 = Cu 2 (Br-BDC) 2 (DMF) 2 (DMF) 3 (H 2 O) 2 : Calcd. C, 36.70; H, 4.47; N, Found C, 37.19; H, 4.24; N, FT-IR: (KBr, cm 1 ): 3455 (br), 3073 (w), 2930 (w), 2808 (w), 1978 (s), 1622 (vs), 1495 (m), 1393 (vs), 1251(w), 1149 (w), 1098(w), 1067 (w), 1037 (w), 914 (w), 833 (m), 772 (m), 742 (w), 680 (w), 568(w). Cu 2 (o-br-m-bdc) 2 (DMF) 2 (H 2 O) 2 (DMF) 2 (MOF-112). An exact amount of 2- bromoisophtalic acid, (o-br-m-bdch 2 ) (17.25 mg, 0.07 mmol), and copper(ii) nitrate hemipentahydrate, Cu(NO 3 ) 2 2.5H 2 O, (16.13 mg, 0.07 mmol) was dissolved in DMF/ethanol (1.5 ml/0.5 ml). The solution was placed in a Pyrex tube (10 mm 8 mm o.d. i.d., 140 mm length). The evacuated tube was sealed and heated to 80 C for 20 h at a rate of 2.0 C/min, then cooled to room temperature at a rate of 1.0 C/min. The resultant green crystals was filtered, and washed with the DMF/ethanol mixture (3 5 ml) to yield MOF-112. Elemental analysis: C 30 H 24 Br 2 O 15 N 4 Cu 2 = Cu 2 (o-br-m-bdc) 2 (DMF) 2 (H 2 O) 2 (DMF) 2 : Calcd C, 35.72; H, 4.07; N, Found C, 36.07; H, 4.07; N, FT-IR: (KBr, cm -1 ): 3435 (br), 2936 (w), 1663 (s), 1622 (vs), 1500 (w), 1439 (m), 1388 (vs), 1255(w), 1180 (w), 1113 (w), 1062 (w), 925 (w), 779 (w), 731 (w), 705 (w), 527(w). NB: The series of compounds were insoluble to most common organic solvents, such as ethanol, methanol, propanol, butanol, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, benzene, acetone, N,N'-dimethylformamide, and N,N'- diethylformamide. 7

8 X-Ray Crystallographic Data for MOF X-Ray Crystallography of MOF-102. A blue, block crystal ( mm) of MOF-102 was coated with a light hydrocarbon-based inert oil and mounted on a standard Bruker SMART APEX CCD-based x-ray diffractometer equipped with a normal focus Mo-target x-ray tube (λ = Å). The x-ray intensities were measured at 153(2) K. Data frames were collected with a scan width of 0.3 in ω and phi with an exposure time of 30 s per frame. The frames were integrated with the Bruker SAINT software package with a narrow frame algorithm (SAINT PLUS, V. 6.01, Bruker Analytical X-ray, Madison, WI). The integration of the data yielded a total of 5,255 reflections to a maximum 2θ value of 55.06, of which 3,840 were independent and 2,031 were greater than 2σ(I). The final cell constants (Table 1) were based on xyz centroids of 803 reflections above 10 σ(i). Analysis of the data showed negligible decay during data collection. Absorption correction was applied for the integrated intensity data by SADABS [Sheldrick, G. M. (1996) SADABS: Program for Empirical Absorption Correction of Area Detector Data (University of Göttingen, Germany)]. The structure was solved by direct methods and the subsequent difference Fourier methods. Refinement processes were carried out with the Bruker SHELXTL (Version 5.10) software package [Sheldrick, G. M. (1997) SHELXTL, V. 5.10; Bruker Analytical X-ray, Madison, WI], using the centrosymmetric space group P( 1) with Z = 1 for the formula. There were two independent half Cl 2 BDC links and a copper atom in general positions. The axial positions of the copper atoms were coordinated with DMF molecules. A DMF molecule was included in the void space as a guest molecule. All nonhydrogen atoms were refined anisotropically. All hydrogen atoms were also included with ideal geometry. Final full matrix least-squares refinement converged to R1 = (I > 2σ(I)) and wr2 = (all data) with GOF =

9 Fig. 3. ORTEP drawing of MOF

10 Table 3. Crystal data and structure refinement for MOF-102 Identification code MOF-102 Empirical formula C28 H32 N4 O12 Cl4 Cu2 Formula weight Temperature 153(2) K Wavelength Å Crystal system Triclinic Space group P(-1) Unit cell dimensions a = (12) Å α= (3). b = (14) Å β= (2). c = (14) Å γ = (3). Volume 965.6(2) Å 3 Z 1 Density (calculated) Mg/m 3 Absorption coefficient mm 1 F(000) 450 Crystal size mm 3 Theta range for data collection 1.98 to Index ranges 8<=h<=12, 13<=k<=13, 14<=l<=10 Reflections collected 5255 Independent reflections 3840 [R(int) = ] Completeness to theta = % Absorption correction SADABS Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data/restraints/parameters 3840/0/226 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 10

11 Table 4. Atomic coordinates ( 10 4 ) and equivalent isotropic displacement parameters (Å ) for MOF-102 [U(eq) is defined as one-third of the trace of the orthogonalized U ij tensor] x y z U(eq) Cu(1) 8388(1) -526(1) -391(1) 22(1) Cl(1) 9231(4) 3262(2) -2628(2) 45(1) Cl(2) 11950(3) 2748(2) 4244(2) 38(1) O(1) 8738(8) 1390(5) -291(6) 33(2) O(2) 11432(8) 2275(5) 331(6) 34(2) O(3) 8598(8) -421(6) 1463(5) 32(2) O(4) 11310(8) 493(6) 2114(5) 32(2) C(1) 10071(12) 2327(8) 17(8) 25(2) C(2) 10072(11) 3740(8) 2(8) 27(2) C(3) 9645(12) 4229(8) -1150(8) 33(2) C(4) 9550(11) 5472(8) -1155(8) 29(2) C(5) 9977(12) 56(7) 2313(8) 21(2) C(6) 9980(10) 69(8) 3698(7) 21(2) C(7) 10875(11) 1220(8) 4654(8) 27(2) C(8) 10895(11) 1145(8) 5931(8) 28(2) O(1S) 5853(8) -1366(6) -1204(6) 35(2) N(1S) 3631(10) -2802(8) -2767(8) 43(2) C(1S) 5130(13) -2366(9) -2094(9) 38(2) C(2S) 2621(14) -2171(13) -2575(13) 71(4) C(3S) 2918(16) -3916(13) -3799(12) 78(4) O(2S) 4093(11) 5136(9) 3185(9) 82(3) N(2S) 4634(14) 6901(11) 2053(13) 83(4) C(4S) 4385(16) 6322(14) 3106(13) 71(4) C(5S) 4560(20) 6019(18) 846(16) 122(7) C(6S) 4908(19) 8347(16) 2127(19) 131(8) 11

12 Table 5. Bond lengths (Å) and angles ( ) for MOF-102 Cu(1)-O(3) 1.957(6) Cu(1)-O(2)# (5) Cu(1)-O(4)# (6) Cu(1)-O(1) 1.964(5) Cu(1)-O(1S) 2.103(6) Cu(1)-Cu(1)# (2) Cl(1)-C(3) 1.748(8) Cl(2)-C(7) 1.727(9) O(1)-C(1) 1.224(10) O(2)-C(1) 1.250(10) O(2)-Cu(1)# (5) O(3)-C(5) 1.263(10) O(4)-C(5) 1.244(10) O(4)-Cu(1)# (6) C(1)-C(2) 1.525(10) C(2)-C(4)# (10) C(2)-C(3) 1.383(11) C(3)-C(4) 1.378(10) C(4)-C(2)# (10) C(5)-C(6) 1.499(10) C(6)-C(8)# (11) C(6)-C(7) 1.407(11) C(7)-C(8) 1.384(11) C(8)-C(6)# (11) O(1S)-C(1S) 1.258(10) N(1S)-C(1S) 1.282(12) N(1S)-C(2S) 1.411(14) N(1S)-C(3S) 1.430(13) O(2S)-C(4S) 1.216(13) N(2S)-C(4S) 1.352(15) N(2S)-C(6S) 1.480(16) N(2S)-C(5S) 1.565(18) O(3)-Cu(1)-O(2)#1 88.6(2) O(3)-Cu(1)-O(4)# (3) O(2)#1-Cu(1)-O(4)#1 89.4(3) O(3)-Cu(1)-O(1) 89.4(2) O(2)#1-Cu(1)-O(1) 167.2(3) O(4)#1-Cu(1)-O(1) 89.8(3) O(3)-Cu(1)-O(1S) 100.3(2) O(2)#1-Cu(1)-O(1S) 94.6(3) O(4)#1-Cu(1)-O(1S) 92.1(2) O(1)-Cu(1)-O(1S) 98.2(2) O(3)-Cu(1)-Cu(1)# (19) O(2)#1-Cu(1)-Cu(1)#1 85.2(2) O(4)#1-Cu(1)-Cu(1)# (19) O(1)-Cu(1)-Cu(1)# (19) O(1S)-Cu(1)-Cu(1)# (18) C(1)-O(1)-Cu(1) 124.2(6) C(1)-O(2)-Cu(1)# (6) C(5)-O(3)-Cu(1) 120.6(6) C(5)-O(4)-Cu(1)# (5) O(1)-C(1)-O(2) 128.4(8) O(1)-C(1)-C(2) 115.9(8) O(2)-C(1)-C(2) 115.7(8) C(4)#2-C(2)-C(3) 119.0(7) C(4)#2-C(2)-C(1) 119.3(7) C(3)-C(2)-C(1) 121.6(7) C(4)-C(3)-C(2) 121.1(7) C(4)-C(3)-Cl(1) 119.3(7) C(2)-C(3)-Cl(1) 119.6(6) C(2)#2-C(4)-C(3) 119.8(7) O(4)-C(5)-O(3) 126.8(8) O(4)-C(5)-C(6) 117.6(8) O(3)-C(5)-C(6) 115.6(8) C(8)#3-C(6)-C(7) 118.5(7) C(8)#3-C(6)-C(5) 118.1(7) 12

13 Table 5 (continued) C(7)-C(6)-C(5) 123.4(7) C(8)-C(7)-C(6) 120.5(8) C(8)-C(7)-Cl(2) 119.2(6) C(6)-C(7)-Cl(2) 120.4(6) C(7)-C(8)-C(6)# (7) C(1S)-O(1S)-Cu(1) 121.7(7) C(1S)-N(1S)-C(2S) 122.0(9) C(1S)-N(1S)-C(3S) 121.3(10) C(2S)-N(1S)-C(3S) 116.6(10) O(1S)-C(1S)-N(1S) 124.9(10) C(4S)-N(2S)-C(6S) 115.9(14) C(4S)-N(2S)-C(5S) 119.3(12) C(6S)-N(2S)-C(5S) 124.8(13) O(2S)-C(4S)-N(2S) 124.1(14) Symmetry transformations used to generate equivalent atoms: #1 x + 2, y, z #2 x + 2, y + 1, z #3 x + 2, y, z

14 Table 6. Anisotropic displacement parameters (Å ) for MOF-102 [the anisotropic displacement factor exponent takes the form: 2π 2 [ h 2 a* 2 U h k a* b* U 12 ]] U 11 U 22 U 33 U 23 U 13 U 12 Cu(1) 46(1) 12(1) 14(1) 8(1) 13(1) 16(1) Cl(1) 95(2) 28(1) 22(1) 7(1) 18(1) 36(1) Cl(2) 67(2) 21(1) 23(1) 9(1) 19(1) 10(1) O(1) 39(4) 14(3) 44(4) 6(3) 9(3) 12(3) O(2) 48(4) 18(3) 36(4) 6(3) 12(3) 15(3) O(3) 46(4) 40(4) 14(3) 6(3) 12(3) 19(3) O(4) 42(4) 40(4) 15(3) 7(3) 13(3) 13(3) C(1) 41(6) 22(5) 15(4) 8(3) 8(4) 17(5) C(2) 54(6) 16(4) 20(4) 8(3) 14(4) 20(4) C(3) 64(7) 18(4) 21(5) 3(4) 10(5) 24(5) C(4) 57(6) 16(4) 22(5) 15(3) 14(4) 22(4) C(5) 42(6) 8(4) 20(4) 6(3) 14(4) 13(4) C(6) 35(5) 20(4) 9(4) 7(3) 11(4) 11(4) C(7) 49(6) 23(4) 14(4) 8(3) 15(4) 16(4) C(8) 48(6) 21(4) 18(4) 2(3) 14(4) 15(4) O(1S) 51(4) 27(3) 33(4) 10(3) 21(3) 16(3) N(1S) 35(5) 42(5) 43(5) 8(4) 7(4) 7(5) C(1S) 51(7) 33(5) 33(6) 13(5) 20(5) 16(5) C(2S) 52(8) 65(8) 90(11) 15(7) 22(7) 16(7) C(3S) 76(10) 69(9) 62(9) 4(7) 3(7) 14(8) O(2S) 100(8) 59(6) 97(8) 44(5) 41(6) 32(6) N(2S) 84(9) 67(7) 106(10) 51(7) 41(7) 28(7) C(4S) 82(10) 66(9) 70(10) 31(7) 32(8) 29(8) C(5S) 138(16) 135(15) 80(12) 31(11) 62(11) 20(13) C(6S) 85(12) 100(12) 220(20) 113(13) 45(12) 47(10) 14

15 Table 7. Hydrogen coordinates ( 10 4 ) and isotropic displacement parameters (Å ) for MOF-102 x y z U(eq) H(4) H(8) H(1SA) H(2SA) H(2SB) H(2SC) H(3SA) H(3SB) H(3SC) H(4SA) H(5SA) H(5SB) H(5SC) H(6SA) H(6SB) H(6SC)

16 X-Ray Crystallography of MOF-103. A rectangular colorless crystal ( mm) of MOF-103 was set on a cryo-loop in a thin layer of inert oil and mounted on a Bruker SMART CCD diffractometer equipped with a normal focus Mo-target x-ray tube (λ = Å) operated at 2,000 W power (50 kv, 40 ma). The x-ray intensities were measured at 158(2) K. Data frames were collected with a scan width of 0.3 in ω and phi with an exposure time of 30 s per frame. The frames were integrated with the SAINT software package with a narrow frame algorithm. The integration of the data yielded 3,162 unique reflections to a maximum 2 value of 52.92, of which 2,234 were greater than 2σ(I). Analysis of the data showed negligible decay during data collection. While an absorption correction was not applied, all data were corrected for the extinction effect. The structure was solved by direct methods and subsequent difference Fourier syntheses and refined with the SHELXTL (Version 5.10) software package, using the space group P2 1 /n with Z = 4 for the formula based on the elemental analysis. All nonhydrogen atoms were refined anisotropically. The DMF and water guest molecules were disordered and their occupancies were refined. The hydrogen atoms were added with ideal geometries. Final full matrix least-squares refinement on F 2 converged to R1 = (F > σ(f)) and wr2 = (all data) with GOF = Additional details are presented in Table 1 and the accompanying text. 16

17 Fig. 4. ORTEP drawing of MOF

18 Table 8. Crystal data and structure refinement for MOF-103 Identification code MOF-103 Empirical formula C13.39 H15.08 N0.95 O7.15 Zn Formula weight Temperature 158(2) K Wavelength Å Crystal system Monoclinic Space group P2(1)/n Unit cell dimensions a = (5) Å α= (3). b = (12) Å β= (3). c = (8) Å γ = (3). Volume (18) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm 1 F(000) 757 Crystal size mm 3 Theta range for data collection 2.03 to Index ranges 9<=h<=9, 0<=k<=21, 0<=l<=15 Reflections collected 3162 Independent reflections 3162 [R(int) = ] Completeness to theta = % Absorption correction None Refinement method Full-matrix least-squares on F 2 Data/restraints/parameters 3162/0/216 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient (9) Largest diff. peak and hole and e.å 3 18

19 Table 9. Atomic coordinates ( 10 4 ) and equivalent isotropic displacement parameters (Å ) for MOF-103 [U(eq) is defined as one-third of the trace of the orthogonalized U ij tensor] x y z U(eq) O(6) 4050(9) 5452(4) 6761(4) 119(3) C(11) 6411(15) 6428(7) 4817(8) 158(6) C(13) 5029(14) 5695(6) 6239(6) 93(3) C(12) 3072(19) 6593(9) 5098(9) 221(8) N(1) 4990(11) 6221(5) 5376(5) 110(3) O 5191(16) 9987(5) 8614(10) 123(6) O' 7690(40) 5603(17) 5720(20) 232(18) O" 6210(40) 5110(15) 6740(20) 74(12) O* 5650(50) 9540(20) 9760(30) 240(20) Zn(1) 11763(1) 4939(1) 9476(1) 15(1) O(1) 10442(3) 5814(2) 8641(2) 28(1) O(2) 7729(4) 5857(2) 9343(2) 30(1) O(3) 5160(4) 9132(2) 6188(2) 31(1) O(4) 7890(3) 9205(1) 5525(2) 26(1) O(5) 13778(3) 4696(2) 8572(2) 27(1) C(1) 8876(5) 6097(2) 8723(3) 24(1) C(2) 8318(5) 6800(2) 8034(3) 23(1) C(3) 6596(5) 7144(2) 8013(3) 30(1) C(4) 4745(6) 7094(3) 8478(5) 59(2) C(5) 4227(6) 7856(3) 7777(5) 61(2) C(6) 6141(5) 7806(2) 7411(3) 29(1) C(7) 7328(5) 8177(2) 6771(3) 22(1) C(8) 9054(5) 7826(2) 6768(3) 30(1) C(9) 9525(5) 7155(2) 7372(3) 30(1) C(10) 6750(5) 8891(2) 6115(3) 23(1) 19

20 Table 10. Bond lengths (Å) and angles ( ) for MOF-103 _ O(6)-C(13) 1.090(10) C(11)-N(1) 1.349(9) C(13)-N(1) 1.396(10) C(12)-N(1) 1.554(12) O-O* 1.64(4) O*-O*#1 1.94(7) Zn(1)-O(5) 1.978(2) Zn(1)-O(2)# (2) Zn(1)-O(1) 2.009(2) Zn(1)-O(4)# (2) Zn(1)-O(3)# (2) Zn(1)-Zn(1)# (8) O(1)-C(1) 1.256(4) O(2)-C(1) 1.258(4) O(2)-Zn(1)# (2) O(3)-C(10) 1.246(4) O(3)-Zn(1)# (2) O(4)-C(10) 1.275(4) O(4)-Zn(1)# (2) C(1)-C(2) 1.501(5) C(2)-C(3) 1.388(5) C(2)-C(9) 1.396(5) C(3)-C(6) 1.372(5) C(3)-C(4) 1.523(5) C(4)-C(5) 1.583(6) C(5)-C(6) 1.515(5) C(6)-C(7) 1.380(5) C(7)-C(8) 1.398(5) C(7)-C(10) 1.497(5) C(8)-C(9) 1.387(5) O(6)-C(13)-N(1) 136.9(11) C(11)-N(1)-C(13) 126.7(10) C(11)-N(1)-C(12) 120.3(10) C(13)-N(1)-C(12) 112.9(8) O-O*-O*#1 80(2) O(5)-Zn(1)-O(2)# (11) O(5)-Zn(1)-O(1) (11) O(2)#2-Zn(1)-O(1) (11) O(5)-Zn(1)-O(4)# (10) O(2)#2-Zn(1)-O(4)# (12) O(1)-Zn(1)-O(4)# (11) O(5)-Zn(1)-O(3)# (11) O(2)#2-Zn(1)-O(3)# (12) O(1)-Zn(1)-O(3)# (12) O(4)#3-Zn(1)-O(3)# (10) O(5)-Zn(1)-Zn(1)# (8) O(2)#2-Zn(1)-Zn(1)# (8) O(1)-Zn(1)-Zn(1)# (8) O(4)#3-Zn(1)-Zn(1)# (7) O(3)#4-Zn(1)-Zn(1)# (7) C(1)-O(1)-Zn(1) 129.9(3) C(1)-O(2)-Zn(1)# (2) C(10)-O(3)-Zn(1)# (3) C(10)-O(4)-Zn(1)# (2) O(1)-C(1)-O(2) 126.3(3) O(1)-C(1)-C(2) 117.4(3) O(2)-C(1)-C(2) 116.3(3) C(3)-C(2)-C(9) 115.6(3) C(3)-C(2)-C(1) 123.0(3) C(9)-C(2)-C(1) 121.4(3) C(6)-C(3)-C(2) 121.9(4) C(6)-C(3)-C(4) 94.0(3) C(2)-C(3)-C(4) 144.0(4) C(3)-C(4)-C(5) 85.7(3) C(6)-C(5)-C(4) 86.4(3) C(3)-C(6)-C(7) 123.4(4) 20

21 Table 10 (continued) C(3)-C(6)-C(5) 93.9(3) C(7)-C(6)-C(5) 142.7(4) C(6)-C(7)-C(8) 115.2(3) C(6)-C(7)-C(10) 121.2(3) C(8)-C(7)-C(10) 123.6(3) C(9)-C(8)-C(7) 121.8(4) C(8)-C(9)-C(2) 122.0(4) O(3)-C(10)-O(4) 124.8(3) O(3)-C(10)-C(7) 116.5(3) O(4)-C(10)-C(7) 118.7(3) Symmetry transformations used to generate equivalent atoms: #1 x + 1, y + 2, z + 2 #2 x + 2, y + 1, z + 2 #3 x + 1/2, y + 3/2, z + 1/2 #4 x + 3/2, y 1/2, z + 3/2 #5 x + 3/2, y + 1/2, z + 3/2 #6 x + 1/2, y + 3/2, z 1/2 21

22 Table 11. Anisotropic displacement parameters (Å ) for MOF-103 [the anisotropic displacement factor exponent takes the form: 2π 2 [ h 2 a* 2 U h k a* b* U 12 ]] U 11 U 22 U 33 U 23 U 13 U 12 O(6) 147(6) 178(6) 34(3) 31(3) 19(3) 91(5) C(11) 181(11) 192(11) 114(8) 64(8) 97(9) 126(10) C(13) 106(7) 122(8) 52(5) 13(5) 3(5) 3(6) C(12) 225(16) 320(20) 113(10) 74(12) 16(10) 126(15) N(1) 141(7) 142(7) 47(4) 2(4) 17(4) 73(6) Zn(1) 15(1) 13(1) 18(1) 0(1) 1(1) 1(1) O(1) 26(1) 24(1) 34(2) 13(1) 2(1) 7(1) O(2) 27(2) 25(2) 40(2) 20(1) 6(1) 4(1) O(3) 23(1) 28(2) 42(2) 18(1) 6(1) 8(1) O(4) 23(1) 22(1) 31(2) 11(1) 0(1) 1(1) O(5) 16(1) 33(2) 32(2) 1(1) 4(1) 3(1) C(1) 24(2) 18(2) 29(2) 4(2) 5(2) 2(2) C(2) 21(2) 18(2) 31(2) 10(2) 1(2) 1(2) C(3) 22(2) 29(2) 39(2) 15(2) 8(2) 4(2) C(4) 35(3) 58(3) 85(4) 44(3) 24(3) 15(2) C(5) 31(3) 58(3) 96(4) 55(3) 28(3) 19(2) C(6) 20(2) 27(2) 40(3) 13(2) 5(2) 3(2) C(7) 20(2) 18(2) 28(2) 6(2) 0(2) 0(2) C(8) 23(2) 27(2) 41(3) 13(2) 9(2) 1(2) C(9) 17(2) 27(2) 47(3) 12(2) 6(2) 7(2) C(10) 22(2) 17(2) 28(2) 4(2) 1(2) 0(2) 22

23 Table 12. Hydrogen coordinates ( 10 4 ) and isotropic displacement parameters (Å ) for MOF-103 x y z U(eq) H(11A) H(11B) H(11C) H(13) H(12A) H(12B) H(12C) H(5) H(5') H(4A) H(4B) H(5A) H(5B) H(8) (10) H(9) (10) 23

24 X-Ray Crystallography of MOF-104. A colorless, plate crystal ( mm) of MOF-104 was coated with Paratone N hydrocarbon oil and mounted on a standard Bruker SMART CCD-based x-ray diffractometer equipped with a normal focus Motarget x-ray tube (λ = Å). The x-ray intensities were measured at 168(2) K. Data frames were collected with a scan width of 0.3 in ω with an exposure time of 10 s per frame. The frames were integrated with the Bruker SAINT software package with a narrow frame algorithm [SAINT: SAX Area-Detector Integration Program, V (1995) Siemens Industrial Automation, Madison, WI]. The integration of the data yielded a total of 5,460 reflections to a maximum 2θ value of of which 2,088 were independent and 1,502 were greater than 3σ(I). The final cell constants were determined from a least-squares refinement based on the measured positions of 2,522 reflections in the range of 3.00 < 2θ < Absorption correction was applied for the integrated intensity data by SADABS. The structure was solved by direct methods and the subsequent difference Fourier methods. Refinement processes were carried out with the TEXAN software package [TEXAN Crystal Structure Analysis Package, Molecular Structure Corporation (1985 & 1992)], using the centrosymmetric space group C2/m with Z = 2 for the formula. All nonhydrogen atoms of the framework were refined anisotropically. The remaining nonhydrogen atoms were refined isotropically. All hydrogen atoms were also included with ideal geometry. Final full matrix least-squares refinement converged to R = (I > 3σ(I)) and Rw = with GOF =

25 Fig. 5. ORTEP drawing of MOF

26 Table 13. Crystal data and structure refinement for MOF-104 Identification code MOF-104 Empirical formula C44 H50 N4 O12 Cl2 Zn2 Formula weight Temperature 168(2) K Wavelength Å Crystal system Monoclinic Space group C2/m Unit cell dimensions a = (4) Å α= b = (5) Å β= (1). c = (4) Å γ = Volume (12) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm 1 F(000) 900 Crystal size mm 3 Theta range for data collection to Index ranges 0<=h<=16, 19<=k<=20, 12<=l<=11 Reflections collected 5460 Independent reflections 2088 [R(int) = 0.035] Absorption correction SADABS Max. and min. transmission 0.62 and 0.85 Refinement method Full-matrix least-squares Data/restraints/parameters 1502/0/138 Goodness-of-fit 2.38 Residuals: R; Rw; Rall 0.058; 0.069; Largest diff. peak and hole 0.95 and 0.54 e.å 3 26

27 Table 14. Positional parameters and B(eq) for MOF-104 atom x y z B(eq) Zn(1) (9) (11) 1.66(2) Cl(1) (14) (12) 0.639(2) 10.3(6) Cl(2) (12) (11) (14) 8.0(4) O(1) (4) (3) (5) 3.26(12) O(2) (4) (3).1033(5) 3.56(13) O(3) (5) (6) 2.38(16) N(1) (8) (7) (11) 2.6(2) C(1) (5) (4) (7) 2.27(16) C(2) (5) (4) (7) 2.27(16) C(3) (6) (4) (7) 3.33(18) C(4) (5) (4) (8) 3.2(2) C(5) (6) (4).0995(7) 3.1(2) C(6) (10) (8) (13) 2.3(3) C(7) (10) (7) (13) 2.9(3) C(8) (12) (9) (15) 4.0(3) C(9) 0.442(3) 0.527(2).134(4) 7.1(11) C(10) (16) (2) 3.9(5) C(11) (8) (12) 3.2(2) C(12) (11) (15) 5.8(3) C(13) 0.227(2) (17) 0.560(3) 7.5(7) C(14) 0.270(2) (15) 0.582(2) 4.7(5) C(15) 0.318(3) 0.225(2) 0.624(3) 4.2(6) C(16) (6) C(17) 0.328(3) 0.295(2) 0.580(4) 6.8(9) C(18) (17) (15) 0.644(2) 2.9(3) C(19) 0.348(2) (15) 0.521(3) 7.8(6) H(1) H(2) H(3)

28 Table 15. Bond lengths (Å) and angles ( ) for MOF-104 Zn(1) Zn(1) 2.919(2) C(3) C(4) 1.562(9) 1 Zn(1) O(1) 2.018(4) 1 C(3) C(5) 1.56(1) 7 Zn(1) O(1) 2.018(4) C(4) C(5) 1.524(9) 1 Zn(1) O(2) 2.040(5) 4 C(7) C(7) 0.86(2) Zn(1) O(2) 2.040(5) C(8) C(8) 1.82(3) Zn(1) O(3) 1.999(6) 1 C(9) C(9) 0.91(7) Cl(1) Cl(2) 1.34(2) 1 C(9) C(10) 1.11(4) 1 Cl(1) C(17) 1.23(4) 1 C(10) C(10) 1.16(4) Cl(1) C(18) 0.64(2) 1 C(10) C(11) 1.64(2) 1 Cl(1) C(19) 1.26(3) 1 C(11) C(12) 0.85(1) 1 Cl(2) C(14) 1.83(3) 1 C(13) C(14) 0.82(3) 1 Cl(2) C(15) 1.07(3) 1 C(13) C(15) 1.55(4) 1 Cl(2) C(16) 2.08(2) 1 C(13) C(16) 1.64(3) 1 Cl(2) C(17) 1.15(4) 1 C(13) C(17) 1.55(5) Cl(2) C(18) 0.74(2) 1 C(13) C(19) 1.12(3) O(1) C(1) 1.254(7) 1 C(14) C(15) 0.76(3) 1 O(2) C(1) 1.243(7) 1 C(14) C(16) 1.15(2) 1 O(3) C(6) 1.32(1) 1 C(14) C(17) 1.76(5) 1 O(3) C(6) 1.32(1) C(14) C(17) 1.74(4) N(1) C(6) 1.34(2) 1 C(14) C(19) 1.84(4) N(1) C(7) 1.43(2) 1 C(15) C(16) 1.36(3) 1 N(1) C(8) 1.52(2) 1 C(15) C(17) 1.28(4) 1 C(1) C(2) 1.497(8) 1 C(15) C(18) 1.55(4) 1 C(2) C(3) 1.546(9) 1 C(16) C(17) 1.32(4) 1 C(2) C(4) 1.562(9) 7 C(16) C(17) 1.32(4) C(2) C(5) 1.558(8) 1 C(17) C(18) 0.84(4) 1 28

29 Table 16. Anisotropic displacement parameters (Å 2 ) for MOF-104 U 11 U 22 U 33 U 23 U 13 U 12 Zn(1) (6) (6) (6) (5) O(1) 0.049(3) 0.040(3) 0.041(3) 0.023(3) 0.025(3) 0.003(3) O(2) 0.044(3) 0.049(3) 0.040(3) 0.030(3) 0.013(3).003(3) O(3) 0.034(4) 0.036(4) 0.024(4) (3) C(1) 0.026(4) 0.021(4) 0.043(5) 0.001(3) 0.017(4) 0.000(3) C(2) 0.029(4) 0.024(4) 0.038(4) 0.009(3) 0.019(3).002(3) C(3) 0.037(4) 0.040(5) 0.048(5) 0.019(4) 0.015(4).008(4) C(4) 0.027(4) 0.025(4) 0.082(6) 0.006(3) 0.033(4) 0.000(4) C(5) 0.050(5) 0.032(4) 0.053(5) 0.020(4) 0.038(4) 0.013(4) 29

30 X-Ray Crystallography of MOF-105. A colorless blade-like crystal ( mm) of MOF-105 was coated with a light hydrocarbon-based inert oil and mounted on a standard Bruker SMART APEX CCD-based x-ray diffractometer equipped with a normal focus Mo-target x-ray tube (λ = Å). The x-ray intensities were measured at 158(2) K. Data frames were collected with a scan width of 0.3 in ω and phi with an exposure time of 30 s per frame. The frames were integrated with the Bruker SAINT software package with a narrow frame algorithm [SAINT PLUS, V. 6.01, Bruker Analytical X-ray, Madison, WI]. The integration of the data yielded a total of 16,114 reflections to a maximum 2θ value of 52.84, of which 3,500 were independent and 2,280 were greater than 2σ(I). The final cell constants (Table 1) were based on xyz centroids of 3,438 reflections above 10σ(I). Analysis of the data showed negligible decay during data collection. Absorption correction was applied for the integrated intensity data by SADABS. The structure was solved by direct methods and the subsequent difference Fourier methods. Refinement processes were carried out with the Bruker SHELXTL (Version 5.10) software package, using the centrosymmetric space group P2 1 /c with Z = 2 for the formula. The axial positions of the copper atoms were coordinated with DMF molecules which filled the void space without guest molecules. All nonhydrogen atoms were refined anisotropically. All hydrogen atoms were also included with ideal geometry. Final full matrix least-squares refinement converged to R1 = (I > 2σ(I)) and wr2 = (all data) with GOF = Additional details are presented in the following table. 30

31 Fig. 6. ORTEP drawing of MOF

32 Table 17. Crystal data and structure refinement for MOF-105 Identification code MOF-105 Empirical formula C33 H33 N3 O11 Zn2 Formula weight Temperature 158(2) K Wavelength Å Crystal system Monoclinic Space group P2(1)/c Unit cell dimensions a = 8.130(2) Å α= 90. b = (5) Å β= (5). c = (4) Å γ = 90. Volume (9) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm 1 F(000) 800 Crystal size mm 3 Theta range for data collection 2.02 to Index ranges 10<=h<=10, 20<=k<=20, 15<=l<=16 Reflections collected Independent reflections 3500 [R(int) = ] Completeness to theta = % Absorption correction SADABS Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data/restraints/parameters 3500/0/198 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient (3) Largest diff. peak and hole and e.å 3 32

33 Table 18. Atomic coordinates ( 10 4 ) and equivalent isotropic displacement parameters (Å ) for MOF-105 [U(eq) is defined as one-third of the trace of the orthogonalized U ij tensor] x y z U(eq) Zn(1) 3729(1) 5033(1) 790(1) 20(1) O(1) 5364(3) 4263(2) 1534(2) 33(1) O(2) 7258(3) 4218(2) 314(2) 34(1) O(3) 12822(3) 918(1) 4955(2) 32(1) O(4) 14717(3) 961(1) 3728(2) 33(1) O(5) 2093(3) 5145(1) 1886(2) 27(1) C(1) 6720(5) 4041(2) 1191(3) 27(1) C(2) 7807(4) 3520(2) 1890(2) 23(1) C(3) 7149(4) 3125(2) 2775(3) 26(1) C(4) 8087(4) 2621(2) 3388(3) 26(1) C(5) 9761(4) 2486(2) 3172(2) 22(1) C(6) 10773(4) 1937(2) 3768(2) 24(1) C(7) 12369(4) 1798(2) 3521(2) 25(1) C(8) 13057(4) 2220(2) 2675(3) 28(1) C(9) 12131(4) 2764(2) 2094(3) 28(1) C(10) 10458(4) 2909(2) 2321(2) 24(1) C(11) 9437(4) 3423(2) 1692(3) 25(1) C(12) 13385(4) 1178(2) 4110(3) 26(1) C(13) 2195(4) 5683(2) 2576(3) 28(1) N(1) 1200(4) 5732(2) 3360(2) 33(1) C(15) 1447(5) 6332(2) 4201(3) 43(1) C(14) 101(6) 5140(3) 3452(4) 74(2) 33

34 Table 19. Bond lengths (Å) and angles ( ) for MOF-105 Zn(1)-O(5) 1.978(2) Zn(1)-O(3)# (2) Zn(1)-O(2)# (2) Zn(1)-O(1) 2.045(2) Zn(1)-O(4)# (2) Zn(1)-Zn(1)# (9) O(1)-C(1) 1.256(4) O(2)-C(1) 1.254(4) O(2)-Zn(1)# (2) O(3)-C(12) 1.266(4) O(3)-Zn(1)# (2) O(4)-C(12) 1.257(4) O(4)-Zn(1)# (2) O(5)-C(13) 1.251(4) C(1)-C(2) 1.502(4) C(2)-C(11) 1.368(4) C(2)-C(3) 1.429(4) C(3)-C(4) 1.357(4) C(4)-C(5) 1.416(5) C(5)-C(6) 1.424(4) C(5)-C(10) 1.428(4) C(6)-C(7) 1.366(4) C(7)-C(8) 1.419(4) C(7)-C(12) 1.498(4) C(8)-C(9) 1.370(4) C(9)-C(10) 1.422(5) C(10)-C(11) 1.415(4) C(13)-N(1) 1.316(4) N(1)-C(14) 1.445(5) N(1)-C(15) 1.469(4) O(5)-Zn(1)-O(3)# (10) O(5)-Zn(1)-O(2)# (9) O(3)#1-Zn(1)-O(2)# (10) O(5)-Zn(1)-O(1) 99.78(10) O(3)#1-Zn(1)-O(1) 89.24(10) O(2)#2-Zn(1)-O(1) (10) O(5)-Zn(1)-O(4)# (9) O(3)#1-Zn(1)-O(4)# (10) O(2)#2-Zn(1)-O(4)# (10) O(1)-Zn(1)-O(4)# (10) O(5)-Zn(1)-Zn(1)# (7) O(3)#1-Zn(1)-Zn(1)# (7) O(2)#2-Zn(1)-Zn(1)# (7) O(1)-Zn(1)-Zn(1)# (7) O(4)#3-Zn(1)-Zn(1)# (7) C(1)-O(1)-Zn(1) 125.5(2) C(1)-O(2)-Zn(1)# (2) C(12)-O(3)-Zn(1)# (2) C(12)-O(4)-Zn(1)# (2) C(13)-O(5)-Zn(1) 122.6(2) O(2)-C(1)-O(1) 125.8(3) O(2)-C(1)-C(2) 116.6(3) O(1)-C(1)-C(2) 117.5(3) C(11)-C(2)-C(3) 119.2(3) C(11)-C(2)-C(1) 120.6(3) C(3)-C(2)-C(1) 120.2(3) C(4)-C(3)-C(2) 121.2(3) C(3)-C(4)-C(5) 120.4(3) C(4)-C(5)-C(6) 122.3(3) C(4)-C(5)-C(10) 119.0(3) C(6)-C(5)-C(10) 118.7(3) C(7)-C(6)-C(5) 121.1(3) C(6)-C(7)-C(8) 120.0(3) C(6)-C(7)-C(12) 120.5(3) C(8)-C(7)-C(12) 119.4(3) C(9)-C(8)-C(7) 120.6(3) 34

35 Table 19 (continued) C(8)-C(9)-C(10) 120.6(3) C(11)-C(10)-C(9) 121.9(3) C(11)-C(10)-C(5) 119.0(3) C(9)-C(10)-C(5) 118.9(3) C(2)-C(11)-C(10) 121.0(3) O(4)-C(12)-O(3) 125.5(3) O(4)-C(12)-C(7) 117.7(3) O(3)-C(12)-C(7) 116.8(3) O(5)-C(13)-N(1) 123.7(3) C(13)-N(1)-C(14) 119.6(3) C(13)-N(1)-C(15) 122.0(3) C(14)-N(1)-C(15) 118.2(3) Symmetry transformations used to generate equivalent atoms: #1 x 1, y + 1/2, z 1/2 #2 x + 1, y + 1, z #3 x + 2, y + 1/2, z + 1/2 #4 x + 1, y + 1/2, z + 1/2 #5 x + 2, y 1/2, z + 1/2 35

36 Table 20. Anisotropic displacement parameters (Å ) for MOF-105 [the anisotropic displacement factor exponent takes the form: -2π 2 [ h 2 a* 2 U h k a* b* U 12 ]] U 11 U 22 U 33 U 23 U 13 U 12 Zn(1) 20(1) 22(1) 17(1) 0(1) 4(1) 0(1) O(1) 29(2) 42(2) 27(1) 3(1) 7(1) 12(1) O(2) 34(2) 40(2) 28(1) 11(1) 4(1) 8(1) O(3) 37(2) 34(1) 24(1) 5(1) 2(1) 12(1) O(4) 28(2) 35(1) 35(1) 9(1) 1(1) 11(1) O(5) 26(1) 34(1) 23(1) 6(1) 2(1) 1(1) C(1) 31(2) 22(2) 27(2) 2(2) 10(2) 1(2) C(2) 24(2) 23(2) 21(2) 2(1) 5(1) 3(2) C(3) 22(2) 28(2) 29(2) 3(2) 2(2) 1(2) C(4) 29(2) 29(2) 21(2) 3(2) 1(1) 0(2) C(5) 25(2) 21(2) 18(2) 1(1) 2(1) 1(1) C(6) 26(2) 24(2) 21(2) 1(1) 3(2) 1(2) C(7) 29(2) 21(2) 22(2) 1(1) 8(2) 1(1) C(8) 23(2) 28(2) 32(2) 4(2) 5(2) 3(2) C(9) 27(2) 28(2) 28(2) 8(2) 1(2) 1(2) C(10) 27(2) 24(2) 20(2) 2(1) 5(1) 0(2) C(11) 29(2) 23(2) 23(2) 3(1) 4(2) 4(2) C(12) 23(2) 22(2) 32(2) 1(2) 9(2) 1(2) C(13) 30(2) 30(2) 25(2) 6(2) 1(2) 2(2) C(15) 56(3) 38(2) 34(2) 10(2) 7(2) 3(2) C(14) 80(4) 83(4) 62(3) 34(3) 42(3) 38(3) 36

37 Table 21. Hydrogen coordinates ( 10 4 ) and isotropic displacement parameters (Å ) for MOF-105 x y z U(eq) H(3) (3) H(4) (3) H(6) (3) H(8) (3) H(9) (3) H(11) (3) H(13) (3) H(15A) (3) H(15B) (3) H(15C) (3) H(14A) (3) H(14B) (3) H(14C) (3) 37

38 X-Ray Crystallography of MOF-106. A yellow rod crystal ( mm) of MOF-106 was coated with a light hydrocarbon-based inert oil and mounted on a standard Bruker SMART APEX CCD-based x-ray diffractometer equipped with a normal focus Mo-target x-ray tube (λ = Å). The x-ray intensities were measured at 153(2) K. Data frames were collected with a scan width of 0.3 in ω and phi with an exposure time of 30 s per frame. The frames were integrated with the Bruker SAINT software package with a narrow frame algorithm [SAINT PLUS, V. 6.01, Bruker Analytical X-ray, Madison, WI]. The integration of the data yielded a total of 13,081 reflections to a maximum 2θ value of 56.62, of which 5,458 were independent and 3,608 were greater than 2σ(I). The final cell constants (Table 1) were based on xyz centroids of 1,707 reflections above 10σ(I). Analysis of the data showed negligible decay during data collection. Absorption correction was not applied for the integrated intensity data. The structure was solved by direct methods and the subsequent difference Fourier methods. Refinement processes were carried out with the Bruker SHELXTL (Version 5.10) software package [Sheldrick, G. M. (1997) SHELXTL, V (Bruker Analytical X-ray, Madison, WI)], using the centrosymmetric space group C2/c with Z = 4 for the formula. There were two independent half Cl 2 BDC links and a copper atom in general positions. The axial positions of the copper atoms were coordinated with DMF molecules. Two DMF and a water molecules were included in the pore as guests. The water (O1W) and one of two DMF molecules shared the same site with partial occupancies. The oxygen atom of the disordered DMF was disordered over two sites with O7 and O7. All nonhydrogen atoms were refined anisotropically. All hydrogen atoms were also included with ideal geometry. Final full-matrix least-squares refinement converged to R1 = (I > 2σ(I)) and wr2 = (all data) with GOF = Additional details are presented in the following table. 38

39 Fig. 7. ORTEP drawing of MOF

40 Table 22. Crystal data and structure refinement for MOF-106 Identification code MOF-106 Empirical formula C44.80 H53.75 Fe2 N5.60 O14 Formula weight Temperature 153(2) K Wavelength Å Crystal system Monoclinic Space group C2/c Unit cell dimensions a = (4) Å α= 90. b = (2) Å β= (2). c = (17) Å γ = 90. Volume (12) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm 1 F(000) 2103 Crystal size mm 3 Theta range for data collection 1.51 to Index ranges 36<=h<=20, 19<=k<=20, 15<=l<=15 Reflections collected Independent reflections 5458 [R(int) = ] Completeness to theta = % Absorption correction None Refinement method Full-matrix least-squares on F 2 Data/restraints/parameters 5458/0/293 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å 3 40

41 Table 23. Atomic coordinates ( 10 4 ) and equivalent isotropic displacement parameters (Å ) for MOF-106 [U(eq) is defined as one-third of the trace of the orthogonalized U ij tensor] x y z U(eq) Fe(1) 2727(1) 2483(1) 1089(1) 16(1) O(1) 2263(2) 1205(3) 775(4) 35(1) O(2) 2609(2) 1175(3) 963(3) 30(1) O(3) 3350(1) 2280(3) 153(3) 33(1) O(4) 3228(1) 2628(3) 2475(3) 26(1) O(5) 2019(1) 2636(3) 1557(3) 25(1) O(6) 646(2) 759(5) 865(5) 78(2) N(1) 3959(2) 2988(4) 3371(4) 32(1) N(2) 894(2) 573(4) 967(5) 44(2) C(1) 2435(2) 803(4) 75(5) 21(1) C(2) 2444(2) 169(3) 48(5) 21(1) C(3) 2314(2) 628(4) 921(5) 24(1) C(4) 2336(2) 1528(4) 946(5) 25(1) C(5) 2495(2) 2015(3) 3(5) 19(1) C(6) 2612(2) 1554(4) 992(5) 21(1) C(7) 2590(2) 643(4) 1021(5) 24(1) C(8) 1647(2) 2746(3) 879(4) 20(1) C(9) 1162(2) 2920(4) 1361(4) 20(1) C(10) 739(3) 3065(7) 689(6) 64(3) C(11) 291(3) 3169(7) 1135(6) 72(3) C(12) 244(2) 3144(4) 2262(5) 24(1) C(13) 667(2) 3044(6) 2926(5) 56(2) C(14) 1124(2) 2927(6) 2493(5) 51(2) C(15) 3671(2) 2816(4) 2470(5) 30(1) C(16) 3772(3) 2980(7) 4456(6) 67(3) C(17) 4489(3) 3165(6) 3316(7) 63(3) C(18) 1301(3) 452(6) 1814(7) 60(2) C(19) 966(3) 634(6) 99(7) 60(2) C(20) 404(2) 699(6) 1369(4) 72(3) N(3) 3977(2) 529(3) 2913(4) 56(2) C(23) 3528(2) 437(3) 3425(4) 66(3) 41

42 Table 23 (continued) C(22) 4409(2) 748(3) 3562(4) 101(5) C(21) 3960(2) 366(3) 1715(4) 96(5) O(7) 4417(2) 936(3) 4471(4) 79(5) O(7') 4784(2) 860(3) 3574(4) 98(6) O(1W) 4112(2) 216(3) 4654(4) 82(10) 42

43 Table 24. Bond lengths (Å) and angles ( ) for MOF-106 Fe(1)-O(2) 2.026(4) Fe(1)-O(1)# (4) Fe(1)-O(5) 2.059(4) Fe(1)-O(4) 2.073(4) Fe(1)-O(3) 2.125(4) Fe(1)-Fe(1)# (14) O(1)-C(1) 1.248(7) O(1)-Fe(1)# (4) O(2)-C(1) 1.266(7) O(3)-C(8)# (6) O(4)-C(15) 1.236(7) O(5)-C(8) 1.256(6) O(6)-C(19) 1.227(9) N(1)-C(15) 1.310(7) N(1)-C(16) 1.436(9) N(1)-C(17) 1.469(8) N(2)-C(19) 1.314(10) N(2)-C(18) 1.453(9) N(2)-C(20) 1.462(7) C(1)-C(2) 1.485(7) C(2)-C(3) 1.379(8) C(2)-C(7) 1.404(8) C(3)-C(4) 1.376(8) C(4)-C(5) 1.400(8) C(5)-C(6) 1.395(8) C(5)-C(5)# (9) C(6)-C(7) 1.392(8) C(8)-C(9) 1.503(7) C(9)-C(10) 1.365(8) C(9)-C(14) 1.372(8) C(10)-C(11) 1.376(9) C(11)-C(12) 1.370(9) C(12)-C(13) 1.352(8) C(12)-C(12)# (11) C(13)-C(14) 1.391(9) N(3)-C(22) N(3)-C(23) N(3)-C(21) C(22)-O(7') C(22)-O(7) O(2)-Fe(1)-O(1)# (15) O(2)-Fe(1)-O(5) 89.24(17) O(1)#1-Fe(1)-O(5) 87.98(18) O(2)-Fe(1)-O(4) (16) O(1)#1-Fe(1)-O(4) 91.53(16) O(5)-Fe(1)-O(4) (15) O(2)-Fe(1)-O(3) 86.82(18) O(1)#1-Fe(1)-O(3) 91.30(19) O(5)-Fe(1)-O(3) (14) O(4)-Fe(1)-O(3) 86.77(15) O(2)-Fe(1)-Fe(1)# (12) O(1)#1-Fe(1)-Fe(1)# (12) O(5)-Fe(1)-Fe(1)# (10) O(4)-Fe(1)-Fe(1)# (12) O(3)-Fe(1)-Fe(1)# (11) C(1)-O(1)-Fe(1)# (4) C(1)-O(2)-Fe(1) 123.5(4) C(8)#1-O(3)-Fe(1) 127.1(4) C(15)-O(4)-Fe(1) 126.5(4) C(8)-O(5)-Fe(1) 123.9(3) C(15)-N(1)-C(16) 121.1(5) C(15)-N(1)-C(17) 121.5(6) C(16)-N(1)-C(17) 117.4(6) C(19)-N(2)-C(18) 121.7(7) C(19)-N(2)-C(20) 121.5(6) C(18)-N(2)-C(20) 116.6(6) 43

44 Table 24 (continued) O(1)-C(1)-O(2) 123.9(5) O(1)-C(1)-C(2) 118.6(6) O(2)-C(1)-C(2) 117.5(5) C(3)-C(2)-C(7) 118.4(5) C(3)-C(2)-C(1) 121.5(6) C(7)-C(2)-C(1) 120.1(5) C(4)-C(3)-C(2) 121.2(5) C(3)-C(4)-C(5) 121.5(5) C(6)-C(5)-C(4) 117.4(4) C(6)-C(5)-C(5)# (7) C(4)-C(5)-C(5)# (7) C(7)-C(6)-C(5) 121.2(5) C(6)-C(7)-C(2) 120.2(5) O(3)#1-C(8)-O(5) 125.0(5) O(3)#1-C(8)-C(9) 117.9(5) O(5)-C(8)-C(9) 117.1(5) C(10)-C(9)-C(14) 117.3(5) C(10)-C(9)-C(8) 121.3(5) C(14)-C(9)-C(8) 121.4(5) C(9)-C(10)-C(11) 120.9(6) C(12)-C(11)-C(10) 122.5(6) C(13)-C(12)-C(11) 116.3(5) C(13)-C(12)-C(12)# (7) C(11)-C(12)-C(12)# (7) C(12)-C(13)-C(14) 122.2(6) C(9)-C(14)-C(13) 120.7(6) O(4)-C(15)-N(1) 124.0(6) O(6)-C(19)-N(2) 126.1(8) C(22)-N(3)-C(23) C(22)-N(3)-C(21) C(23)-N(3)-C(21) O(7')-C(22)-N(3) O(7)-C(22)-N(3) Symmetry transformations used to generate equivalent atoms: #1 x + 1/2, y + 1/2, z #2 x + 1/2, y 1/2, z #3 x, y, z + 1/2 44

45 Table 25. Anisotropic displacement parameters (Å ) for MOF-106 [the anisotropic displacement factor exponent takes the form: 2π 2 [ h 2 a* 2 U h k a* b* U 12 ]] U 11 U 22 U 33 U 23 U 13 U 12 Fe(1) 18(1) 13(1) 17(1) 2(1) 3(1) 1(1) O(1) 50(3) 24(2) 31(2) 11(2) 8(2) 1(2) O(2) 52(3) 14(2) 25(2) 1(2) 1(2) 1(2) O(3) 23(2) 59(3) 18(2) 3(2) 5(2) 7(2) O(4) 24(2) 27(2) 25(2) 4(2) 1(2) 1(2) O(5) 20(2) 34(3) 22(2) 6(2) 3(2) 0(2) O(6) 68(4) 108(6) 57(4) 4(4) 16(3) 17(4) N(1) 19(3) 48(3) 27(3) 5(2) 4(2) 4(2) N(2) 35(3) 46(4) 50(4) 2(3) 4(3) 6(3) C(1) 12(3) 21(3) 32(3) 2(3) 12(2) 1(2) C(2) 23(3) 14(2) 28(3) 0(3) 6(2) 1(2) C(3) 33(3) 18(3) 21(3) 4(2) 5(3) 4(3) C(4) 40(4) 18(3) 17(3) 2(2) 3(3) 6(3) C(5) 21(2) 14(2) 22(2) 3(3) 2(2) 1(3) C(6) 26(3) 18(3) 19(3) 1(2) 2(2) 3(2) C(7) 29(3) 22(3) 20(3) 4(2) 2(2) 0(2) C(8) 20(3) 21(3) 19(3) 1(2) 1(2) 1(2) C(9) 19(3) 20(3) 22(3) 0(2) 8(2) 1(2) C(10) 28(4) 147(9) 19(3) 7(4) 7(3) 27(5) C(11) 18(4) 172(10) 26(4) 13(5) 1(3) 22(5) C(12) 22(3) 24(3) 25(3) 1(2) 6(2) 0(2) C(13) 23(4) 126(8) 19(3) 12(4) 4(3) 1(4) C(14) 16(3) 113(7) 23(3) 16(4) 1(3) 6(4) C(15) 28(3) 41(4) 20(3) 2(3) 4(2) 1(3) C(16) 41(5) 127(9) 31(4) 5(5) 5(3) 19(5) C(17) 37(4) 101(7) 48(5) 13(5) 7(4) 19(5) C(18) 60(5) 64(6) 55(5) 15(4) 1(4) 4(4) C(19) 49(5) 69(6) 63(6) 9(5) 9(4) 10(4) C(20) 47(5) 85(7) 87(7) 23(6) 20(5) 8(5) N(3) 58(6) 40(5) 67(6) 8(4) 14(4) 8(4) C(23) 67(8) 59(7) 76(8) 1(6) 25(6) 8(6) C(22) 52(8) 69(9) 180(17) 25(10) 7(9) 5(7) C(21) 116(12) 75(9) 97(11) 1(8) 0(9) 36(9) 45