SUPPORTING INFORMATION

Generic Post-Functionalization Route from Amino-Derived Metal-Organic Frameworks

Marie Savonnet, Delphine Bazer-Bachi, Nicolas Bats, Erwann Jeanneau, Vincent Lecocq, Catherine Pinel, David Farrusseng* Universit Lyon 1 , IRCELYON, Institut de recherches sur la catalyse et lenvironnement de Lyon, UMR 5256 CNRS;2 avenue Albert Einstein; F-69626 Villeurbanne Cedex, France, IFP-Lyon, BP n3, 69360, Solaize,France, Universit Lyon1, Centre de Diffractomtrie, 69629 Villeurbanne Cedex, France Chemicals General S1- Experimental Details for the Synthesis of DMOF-NH2 S2 Effect of solvent guest inclusion on powder X-ray Diffraction of DMOF-NH2 S3 -Experimental Details for the Post-Functionalization of DMOF-NH2 S4- Kinetic of DMOF-N3 formation S5 - Experimental Details for the Synthesis of MIL-68(In)-NH2 S6 - Experimental Details for the Post-Functionalization of MIL-68(In)-NH2

Chemicals All chemicals were used as received without any further purification: N,Ndimethylformamide, DMF (Aldrich, 99.8%), Zinc nitrate, Zn(NO3)24H2O (Merck, 98.5%), 2-aminoterephthalic acid, NH2-bdc (Alfa Aesar, 99%), dimethyl-2-

aminoterephthalate (Aldrich, 97%), dichloromethane, CH2Cl2 (Acros Organics, 99.99%), Indium nitrate, In(NO3).4H2O (Alfa Aesar, 99.99%), 1,4-diazabicyclo[2.2.2] octane, DABCO (Aldrich, 98%), THF (Aldrich, 99%), tBuONO (Aldrich), TMSN3 (Aldrich, 99.5%), tetrakis(acetonitrile)copper(I)hexafluoro-phosphate (CuI(CH3CN)4PF6) (Aldrich), phenylacetylene (Aldrich, 98%), DCl (Aldrich, 99%D), DMSO-d6 (Eurisotop, 99.8%D).

General NMR spectra were recorded on a Bruker Avance 250 spectrometer operating at 250 MHz for 1H. The following abbreviations are used: s, singlet; d, doublet; t, triplet; m, multiplet. IR spectra were recorded on a Fourier Transform Vector 22 Bruker spectrometer in KBr pellets in the 400-4000 cm-1 region. The following abbreviations are used: s, strong; m, medium; w, weak; br, broad. Powder X-ray diffraction patterns were recorded using a Bruker D5005 diffractometer (BraggBrentano geometry, graphite monochromator, Cu K radiation). N2 isotherms at 77K were performed using a BELSORP-max (BEL Japan) and samples were desorbed one night at 100C under vacuum. The thermogravimetric analyses have been carried out on a SETARAM type Setsys Evolution 12 apparatus (heating rate of 2 C min-1) under a pure air flow coupled with a mass spectrometer PFEIFFER, type Omnistar.

S1 - Experimental Details for the Synthesis of DMOF-NH2 Zn(NO3)24H2O (0.781 g, 3.00 mmol) and 2-amino-1,4-benzenedicarboxylic acid (NH2-bdc, 0.554 g, 3.03 mmol) were dissolved in 75 mL of dimethylformamide (DMF). DABCO (0.542 g, 4.815 mmol) was then added to the solution, which immediately generated a large amount of white precipitate. The mixture was filtered using a Pyrex glass funnel of fine porosity. The powder was washed with 3 8 mL of DMF followed by 3 8 mL of CH2Cl2. The powder was then soaked in 10 mL of CH2Cl2 for three days with fresh CH2Cl2 added every 24 h. After three days of soaking, the powder was dried under vacuum at room temperature for one night. The mass of dried DMOF-NH2 obtained was 300 mg.
1

H NMR 250 MHz, (DCl/D2O/DMSO-d6) : 7.13 (d, 1H, J = 8.3Hz); 7.47 (s, 1H); 7.79 (d,

1H, J = 8.3Hz), 3.52 (s, 6.68H, DABCO) Relative concentration of NH2-bdc and DABCO in DMOF-NH2: 1:0.56. (Expected value: 1:0.5) IR data (KBr pellet), (cm-1): 3456 (br), 3345 (br), 2952 (w), 2878 (w), 1666(s), 1632 (s), 1577 (s), 1496 (s), 1435 (s), 1376 (s), 1256 (m), 1102 (m), 1056 (w), 1015 (w), 834 (w), 810 (w), 772 (m), 704 (w), 661 (w), 593 (w).

Figure 1: SEM photograph of the DMOF-NH2 powder.

S2 - Effect of solvent guest insertion on the powder X-Ray diffraction of DMOF-NH2 DMOF-NH2 was obtained as indicated in S1. After soaking in THF or THF/CH2Cl2, DMOFNH2 is less XRD crystalline. Drop of surface areas (1320 to 110 m/g) and microporous volumes from 0.54 to 0.02 cm3/g is observed.

10

20

30

2 /

Figure 2: Powder X-ray diffraction patterns of (black) DMOF-NH2, (red) DMOF-NH2 soaked in THF and (blue) DMOF-NH2 soaked in THF and then in CH2Cl2.

S3 - Experimental Details for the Post-Functionalization of DMOF-NH2 In a typical synthesis, the freshly dried DMOF-NH2 (80 mg, 0.27 mmol equiv of -NH2) was placed into a vial (10 mL capacity) with 3.0 mL of THF, 0.22 mL (1.84 mmol, 7 eq) of tBuONO and 0.2 mL (1.51 mmol, 6 eq) of TMSN3. The sample was left to react for one night at room temperature to produce the azide intermediate corresponding compound .The reaction was quenched by decanting the solvent. Excess reactants were removed by washing three times in THF followed by three times in CH2Cl2. Drying at room temperature yielded of yellow powder of DMOF-N3. The mass of dried DMOF-N3 obtained was 65 mg (for characterization purposes).

COOH N3

COOH

Crystal data for DMOF-N3 [Zn2(C8H4O4N3)2(C6H12N2)]: quadratic system, P4/m with a = b = 10.837 , c = 9.614 and alpha=beta=gamma=90. Crystal data for DMOF-1 [Zn2(C8H4O4)2(C6H12N2)]: tetragonal, P4/m, a= b = 10.929 c=9.608 (Angew. Chem. Int. Ed. 2004, 43, 5033 5036).
1

H NMR 250 MHz, (DCl/D2O/DMSO-d6) : 7.73-7.83 (m, 3H, ArH), 3.56 (s, 6.5H,

DABCO). IR data (KBr pellet), (cm-1): 3430 (br), 3122 (w), 2123(s), 1626 (s), 1484 (w), 1383 (s), 1279 (m), 1167 (w), 1053 (s), 987 (w), 891 (w), 842 (m), 801 (s), 770 (s), 716 (w), 687 (w), 660 (w), 615 (w), 537 (w).

One pot post-functionalization of DMOF-NH2 In a typical synthesis, the freshly dried DMOF-NH2 (80 mg, 0.27 mmol equiv of -NH2) was placed into a vial (10 mL capacity) with 3.0 mL of THF, 0.22 mL (1.84 mmol, 7 eq) of tBuONO and 0.2 mL (1.51 mmol, 6 eq) of TMSN3. The sample was left to react for one night at room temperature to produce the azide intermediate corresponding compound. Phenylacetylene (0.96 mL, 8.8 mmol, 36 eq) and an amount of CuI(CH3CN)4PF6) (48 mg, 0.26 mmol, 1 eq) in 1 mL of THF were added and the mixture was stirred continuously for 24 h. After decantation, the supernate was removed. The solid was washed three times by THF (x 8 ml) and three times by CH2Cl2 (x 8 ml) in order to remove unreactive substrates. The solid was then dried under vacuum at room temperature to yield the final yellow compound, DMOF-fun. The mass of dried DMOF-fun obtained was 60 mg.
5 6 7 4 3 COOH 9 8

COOH N N 1 2

H NMR 250 MHz, (DCl/D2O/DMSO-d6) : 9.14 (s, 1H, H4), 8.18 (m, 2H, H3, H2), 8.03 (d,

1H, J= 8Hz, H1), 7.92 (d, 2H, J= 7Hz, H5, H9), 7.45 (m, 3H, H6, H7, H8), 3.52 (s, 6H, DABCO)
13

C NMR, 62.8 MHz, (DCl/D2O/DMSO-d6) : 122.8, 125.2, 125.6, 126.4, 128.2, 128.9, 129,

130.1, 130.4, 130.9, 132.1, 134.1, 135.1, 146.6, 165.4, 166 IR data (KBr pellet), (cm-1): 3416 (br), 3140 (w), 3053 (w), 1605 (s), 1463 (w), 1383 (s), 1298 (w), 1157 (m), 1053 (w), 915 (w), 839 (s), 767 (s), 695 (s), 558 (w).

Elemental analysis for as-modified DMOF-fun (90%) [Zn2(C16H9O4N3)1,8(C8H3O4N3)0,2(C6H12N2)] 0.8CH2Cl2 Calculated: Zn 14.33, C 49.21, H 3.35, N 12.35; Found: Zn 14.29, C 46.46, H 3.24, N 12.58, Cu: 0.64 TGA data: calculated weight loss for 0.8 CH2Cl2: 8.1%; found: 8.1%. Elementary analysis shows that 0.64% of Cu remains in the DMOF-fun with 90% of grafting rate. It corresponds to 3 Cu for 100 triazolate functions.

10

20

30

40

2 /

Figure 3: Powder X-ray diffraction patterns of (red) DMOF-NH2, (black) DMOF-N3 and (blue) DMOF-fun.

4000

3500

wavenumber 3000 2500 (cm-1) 2000

1500

1000

500

Figure 4: IR spectra of (red) DMOF-NH2 and (black) DMOF-N3, (blue) DMOF-fun

Molecular Modelling The DMOF functionalized structure has been obtained starting from the crystallographic data of DMOF-1. The NH2 groups of DMOF-1 were replaced with (4-phenyl-1,2,3-triazol-1-yl) groups. In order to relax the obtained structure, a geometric optimization followed by a NPT Molecular Dynamics simulation has been performed. The Universal Force Field (UFF) (A. K. Rappe, C. J. Casewit, K. S. Colwell, W. A. Goddard, W. M. Skiff; J. Am. Chem. Soc. 1992,

114, 10024-10035) combined with the self consistent charge equilibration method (Qeq) (A.K. Rappe, W.A. Goddard; J. Phys. Chem. 1991, 95, 3358) as implemented in the Accelrys MS Forcite package was used to mimic the energetic interactions of the system.

Figure 5: Modelling of DMOF-fun (100% grafting)

In order to estimate the sterical demand caused by the introduction of the 4-phenyl-1,2,3triazol-1-yl groups, the different energetic contributions where compared to those obtained for the DMOF-1 at the end of a geometrical optimization employing the same methodology as in the case of the DMOF functionalized.

DMOF-1 Intramolecular Energy (kcal/mol) Van der Waals (kcal/mol) Electrostatic Energy (kcal/mol) 2555 221 -3033

DMOF-fun 3446 133 -2666

891 (+35 %) * -88 (-40 %) 367 (+12 %)

Table 1: Energetic contributions for DMOF-1 and DMOF-fun after geometric optimization allowing cell deformation. * Without subtracting the intramolecular interactions corresponding to the 1,2,3-triazol-1-yl groups.

The cell parameters obtained for both materials at the end of the respective geometric optimizations are as well compared in Table 2:

Lx () DMOF-1 DMOF-fun 20.889 20.813

Ly () 20.785 20.810

Lz () 19.109 19.001

Table 2: cell parameters for DMOF-1 and DMOF-functionalized after geometric optimization allowing cell deformation.

As it can be expected the functionalization causes an increment of the intramolecular energy (35%) at the same time that it generates a slightly higher electrostatic repulsion (10%). In the first case, it should be stressed that the totality of these increments cannot be attributed to sterical effects since an important part comes already from the addition of the new intramolecular interactions of the new groups. In order to account for this effect the intramolecular energy of the 1,2,3-triazol-1-yl groups has been computed separately following the previously described methodology. Once this correction has been done the increment obtained is only 126 kcal/mol (5%). These values seem quite reasonable taking into account the size of the 4-phenyl-1,2,3-triazol-1-yl groups. In addition, no significant changes are observed for the cell parameters confirming the feasibility of a complete functionalization.

Figure 6: Positive mode MS performed after digestion of DMOF-fun

Degree of modification (%) 0 15 40 75 100

BET surface area (m/g) 1320 485 400 310 244

Microporous volume (m3/g) 0.54 0.18 0.15 0.10 0.08

Figure 7: N2 isotherm at 77K of DMOF-fun at different degrees of modification

100 90 80 Degree of modification (%) 70 60 50 40 30 20 10 0 0 5 10 Time (h) 15 20

Figure 8: Kinetic of DMOF-fun (90%) formation.

Synthesis of the corresponding linkers in solution

COOMe NH2 THF tBuONO TMSN3 COOMe COOMe COOMe N N THF N

COOMe N3

Phenylacetylene Cu(ACN)4PF6 COOMe

The same protocol was applied to dimethyl-2-aminoterephthalate in solution in order to obtain reference 1H NMR spectra. Dimethyl-2-aminoterephthalate (0.190 g, 0.91 mmol) was dissolved in THF (4 mL) in a 25 mL round-bottomed flask and cooled to 0C in an ice bath. To this stirred mixture was added tBuONO (141 mg, 0.16 mL, 1.37 mmol), followed by a dropwise addition of TMSN3 (126 mg, 0.14 mL, 1.10 mmol). The resulting solution was stirred at room temperature for one night. Phenylacetylene (140 mg, 0.150 mL, 1.37 mmol) and CuI(CH3CN)4PF6 (48 mg, 0.26 mmol) were then added, and this mixture was stirred overnight at room temperature. The

mixture was concentrated under vacuum and the organics were extracted by CH2Cl2 and washed with water, saturated NaHCO3 (aq) and brine. After drying over Na2SO4, the solvent was taken off under reduced pressure. The yield obtained was 80%.
11 COOMe N N 1 2 3 COOMe 10 4 9 8 5 6 7

H NMR 250 MHz, (DMSO-d6) : 9.22 (s, 1H, H4), 8.24 (d, J= 7Hz, 2H, H3, H2), 8.07 (d, 1H,

J= 8.5Hz, H1), 7.95 (d, 2H, J= 8 Hz, H5, H9), 7.45 (m, 3H, H6, H7, H8), 3.93 (s, 3H, H10), 3.69 (s, 3H11) IR data (KBr pellet), (cm-1): 3140 (w), 2960 (w), 2841 (w), 1737 (s), 1639 (w), 1575 (w), 1454 (m), 1400 (m), 1291 (m), 1250 (m), 1084 (s), 798 (m), 746 (m), 682 (m), 488 (w)

9,5

9,0

8,5

8,0

7,5

7,0

ppm

Figure 9: 1H NMR spectra of (black) corresponding linker in solution and (red) digested DMOF-fun.

S4- Kinetic of DMOF-N3 formation DMOF-NH2 (80 mg, 0.27 mmol equiv of -NH2) was placed into a vial (10 mL capacity) with 3.0 mL of THF, 0.22 mL (1.84 mmol, 7 eq) of tBuONO and 0.2 mL (1.51 mmol, 6 eq) of TMSN3. The sample was left to react for 24h at room temperature with different samplings (at 2.5, 5, 8.5, 12 and 24h).

100

80

Conversion (%)

60

40

20

0 0 5 10 15 20 25

Time (h)

Figure 10: Kinetic of DMOF-N3 formation.

S5 - Experimental Details for the Synthesis of MIL-68(In)-NH2 MIL-68(In)-NH2 was obtained by precipitation reaction in a Pyrex beaker (capacity 100 mL) of a mixture of 4.82 mL (4.14 mmol) of 0.86 M of indium nitrate in DMF and 10.06 mL (3.32 mmol) of 0.33 M 2-aminoterephthalic acid (NH2-bdc) in DMF. The reaction mixture was stirred for 5 minutes then 4.83 mL (6.67 mmol) of 1.38 M 4-diazabicyclo[2.2.2] octane (DABCO) in DMF were added. The reaction mixture was stirred for 120 minutes at room temperature. The obtained precipitate was washed with DMF at 160 C and soaked in dichloromethane during 24h. The mass of dried MIL-68(In)-NH2 obtained was 880 mg. Crystal data of MIL-68(In)-NH2: orthorhombic system, Cmcm with a = 21.804 ; b = 37.517 ; c = 7.207 and alpha=beta=gamma=90. Crystal data of MIL-68(In): orthorhombic system, Cmcm with a = 21.7739 ; b = 37.677 ; c = 7.233 and alpha=beta=gamma=90 (Inorg. Chem. 2008, 47, 11892-11901).
1

H NMR 250 MHz, (DCl/D2O/DMSO-d6) : 7.80 (d, 1H, J = 8.3Hz), 7.44 (s, 1H), 7.15 (d,

1H, J = 8.3Hz)

IR data (KBr pellet), (cm-1): 3487 (br), 3379(br), 1556(s), 1434 (s), 1381 (s), 1366 (w), 1256 (m), 1144(w), 1042 (w), 966 (w), 829 (w), 770 (m), 550 (w)

10

2 /

20

30

Figure 11: Powder X-ray diffraction patterns simulated (red) from MIL-68(In).cif file (Inorg. Chem. 2008, 47, 11892-11901) and (black) experimental MIL-68(In)-NH2.

S6 - Experimental Details for the Post-Functionalization of MIL-68(In)-NH2 In a typical synthesis, the freshly dried MIL-68(In)-NH2 (80 mg, 0.26 mmol equiv of -NH2) was placed into a vial (10 mL capacity) with 3.0 mL of solvent (THF) and 1.48 mL (12.48 mmol, 48 eq) of tBuONO and 1.3 mL (9.88 mmol, 38 eq) of TMSN3. The sample was left to react 6 hours at room temperature to produce the azide MOF. The reaction was quenched by decanting the solvent. Excess reactants were removed by washing three times in THF followed by three times in CH2Cl2. Drying at room temperature yielded a yellow powder of MIL-68(In)-N3. The mass of dried MIL-68(In)-N3 obtained was 70 mg (for characterization purposes). Crystal data: orthorhombic system, Cmcm with a = 21.855 ; b = 37.433 ; c = 7.209 and alpha=beta=gamma=90.
1

H NMR 250 MHz, (DCl/D2O/DMSO-d6) : 7.73-7.83 (m, 3H, ArH)

IR data (KBr pellet), (cm-1): 3414 (br), 2123 (s), 1569 (s), 1495 (w), 1384 (s), 1279 (m), 1153 (w), 1085 (w), 798 (w), 769 (s), 657 (w), 552 (m). One pot post-functionalization of MIL-68(In)-NH2 In a typical synthesis, the freshly dried MIL-68(In)-NH2 (80 mg, 0.26 mmol equiv of -NH2) was placed into a vial (10 mL capacity) with 3.0 mL of solvent (THF) and 1.48 mL (12.48 mmol, 48 eq) of tBuONO and 1.3 mL (9.88 mmol, 38 eq) of TMSN3. The sample was left to react 6 hours at room temperature to produce the azide MOF. Phenylacetylene (1.92 mL, 17.6 mmol, 74 eq) and an amount of CuI(CH3CN)4PF6) (96 mg, 0.52 mmol, 2.2 eq) in 1.5 mL of THF were added and the mixture was stirred continuously for 24 h. After decantation, the supernatant was removed. The solid was washed three times by THF (x 8 ml) and three times by CH2Cl2 (x 8 ml) in order to remove unreactive substrates. Drying under vacuum at room temperature yielded a yellow powder of MIL-68(In)-fun. The mass of dried MIL-68(In)-fun obtained was 60 mg.
1

H NMR 250 MHz, (DCl/D2O/DMSO-d6) : 9.13 (s, 1H, H4), 8.20 (d, 1H, J= 6.5Hz, H2), 8.14

(s, 1H, H3), 8.04 (d, 1H, J= 8Hz, H1), 7.92 (d, 2H, J= 6Hz, H5, H9), 7.42 (m, 3H, H6, H7, H8 + 15H excess of phenylacetylene blocked into the pores). IR data (KBr pellet), (cm-1): 3422(br), 3049 (w), 2980 (w), 2120 (w), 1570 (s), 1482 (m), 1405 (s), 1298 (m), 1143 (m), 1042 (m), 898 (w), 836 (w), 745 (m), 683 (m), 566 (w), 512 (w).

4000

3500

3000

2500

2000

1500

1000

500

Wavenumber (cm-1)

Figure 12: IR spectra of (red) MIL-68(In)-NH2 , (black) MIL-68(In)-N3 and (blue) Mil-68(In)-fun

9,0

8,5

8,0

7,5

7,0

6,5

6,0

ppm

Figure 13: 1H NMR spectra of (red) MIL-68(In)-NH2 , (black) MIL-68(In)-N3 and (blue) Mil-68(In)-fun

9,5

9,0

8,5

8,0

ppm

7,5

7,0

6,5

6,0

Figure 14: 1H NMR spectra of (red) MIL-68(In)-NH2 , (black) MIL-68(In)-N3 and (blue) Mil-68(In)-fun (40%)

In the DMOF system, all substrate in excess can easily be removed by washing treatments (3xTHF + 3xCH2Cl2). In contrast, for high grafting rate (>90%) in MIL-68(In), excess of substrate are trapped in the channels (S6, Fig13). However, for lower grafting rate (40%) as it

is shown in S6, Fig.14, all substrate in excess can be removed by washing treatments. This difference between DMOF and MIL-68(In) can be explained by the different porous structure. The DMOF has a 3 dimensional pore structure whereas MIL-68(In) has a 1D channel structure. Therefore, it is much easier to evacuate guest molecules in DMOF although it has a smaller pore size. For MIL-68(In), when the grafting rate is high (90%), the guest molecules are trapped into the channels which become tight due to the high sterical demands. We believe that the aromatic ring do not rotate anymore. For much lower grafting rate (S6, Fig.14), we think that substrates can still pass from one channel to an other to allow a complete evacuation of the excess. This hypothesis is supported by N2 physisorption measurements at 77K on MIL-68(In) systems (S6, Fig 16). It clearly shows a marked drop of the surface area and micropore volume when the degree of modification goes from 50% to 80%.

10

20

30

40

2 /

Figure 15: Powder X-ray diffraction patterns of (red) MIL-68(In)-NH2, (black) MIL-68(In)-N3 and (blue) MIL68(In)-fun.

Degree of modification (%) 0 50 80

BET surface area (m/g) 1260 571 120

Microporous volume (m3/g) 0.48 0.21 0.03

Figure 16: N2 isotherm at 77K of MIL-68(In)-fun at different degrees of modification

0 -10 -20 -30

Weight loss (%)

-40 -50 -60 -70 -80 -90 -100 0 200 400 600

Temperature C

Figure 17: Thermogravimetric analysis (TGA) of as-synthesized DMOF-NH2

The TGA data indicate that DMOF-NH2 loses H2O and DMF (23.8%) in the temperature range of 100200C, and the resulting porous framework (57.7%) starts to decompose after 300C.

0 -10 -20 -30

Weight loss (%)

-40 -50 -60 -70 -80 -90 -100 0 200 400 600

Temperature (C)

Figure 18: Thermogravimetric analysis (TGA) of as-modified DMOF-fun (50%)

The TGA data indicate that DMOF-fun loses its guest molecules CH3CN and CH2Cl2 (8.1%) in the temperature range of 15120C, then the unstable azide groups are decomposed between 120-220C (4%). The resulting porous framework (63%) starts to decompose after 220C.
0 -10 -20 -30

Weight loss (%)

-40 -50 -60 -70 -80 -90 -100 0 200 400 600

Temperature (C)

Figure 19: Thermogravimetric analysis (TGA) of as-synthesized MIL-68(In)-NH2

The TGA data indicate that MIL-68(In)-NH2 loses its guest molecules CH2Cl2 (9.1%) in the temperature range of 15120C, and the resulting porous framework (49%) starts to decompose after 350C.

0 -10 -20 -30

Weight loss (%)

-40 -50 -60 -70 -80 -90 -100 0 200 400 600

temperature (C)

Figure 20: Thermogravimetric analysis (TGA) of as-modified MIL-68(In)-fun (30%)

The TGA data indicate that MIL-68(In)-fun loses its guest molecules H2O (3.5%) in the temperature range of 15120C, then the unstable azide groups are decomposed between 120220C (8%). The resulting porous framework (52%) starts to decompose after 270C.