Supporting information Flexible porous coordination polymers constructed by 1,2-bis(4-pyridyl)hydrazine via solvothermal in situ reduction of 4,4 -Azopyridine Xiao-Min Liu, Lin-Hua Xie, Jian-Bin Lin, Rui-Biao Lin, Jie-Peng Zhang* and Xiao-Ming Chen MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China E-mail: zhangjp7@mail.sysu.edu.cn. 1
Supplementary Index Figure S1. LC-MS (ESI) spectrum for the starting material 4,4 -azopyridine (azpy). Figure S2. 1 H-NMR spectrum for azpy. Figure S3. LC-MS (ESI) spectrum for acid digested 1a. Figure S4. Coordination environments of each independent Zn 2+ in 1a and 1b. Table S1. Zn-O and Zn-N bond lengths in 1a and 1b. Figure S5. Conformations of bphy ligands in 1a and 1b. Table S2. N-N bond lengths and C-N-N-C torsion angles in 1a and 1b. Figure S6. Coordination environments of Zn for 2a and 2b. Table S3. Zn-O and Zn-N bond lengths in 2a and 2b. Figure S7. Conformations of bphy ligands in 2a and 2b. Table S4. N-N bond lengths and C-N-N-C torsion angles in 2a and 2b. Figure S8. PXRD patterns for as-synthesized products. Figure S9. TG curves of 1a, 1b, 2a and 2b. Figure S10. PXRD patterns for activated and regenerated phase of 1a/1b. Figure S11. PXRD patterns for activated and regenerated phase of 2a/2b. Figure S12. PXRD patterns for 2 before adsorption and after desorption. 2
1_091125111950 #144-148 RT: 4.28-4.40 AV: 5 SB: 25 3.24-4.13 NL: 3.34E5 T: + p Full ms [ 50.00-2000.00] 100 185.2 95 90 85 80 75 70 65 Relative Abundance 60 55 50 45 40 35 30 25 20 15 10 5 0 52.7 186.2 291.2 225.8 79.0 224.7 254.9 292.1 75.1 81.5 94.9 105.7 117.1 139.3 144.9 157.1 173.0 201.2 229.1 251.3 263.1 284.9 60 80 100 120 140 160 180 200 220 240 260 280 300 m/z Figure S1. LC-MS (ESI) spectrum for starting material 4,4 -azopyridine (azpy). m/z = 185.2 (M+H + ). 0.000 2.496 3.310 7.784 7.804 8.861 8.881 4.00 4.03 10.0 ppm (t1) 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0 Figure S2. 1 H-NMR spectrum (300 MHz, [D 6 ] DMSO) [ppm] for 4,4 -azopyridine (azpy): δ = 8.87 (d, J = 6Hz, 4H, Ar-H), δ = 7.79 (d, J = 6Hz, 4H, Ar-H). (δ = 3.3 (H 2 O) and δ = 2.5 (DMSO)). 3
6.9-4 #27-29 RT: 0.79-0.85 AV: 3 SB: 4 0.43-0.52 NL: 1.92E6 T: + p Full ms [ 50.00-2000.00] 100 187.2 95 90 85 80 75 70 65 Relative Abundance 60 55 50 45 40 35 30 25 20 15 188.2 10 5 0 218.7 232.8 264.8 278.9 188.9 205.0 236.8 214.9 246.7 268.7 280.9 146.2 152.0 156.7 170.1 176.9 185.1 227.5 260.9 294.3 121.7 131.4 138.7 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 m/z Figure S3. LC-MS (ESI) spectrum for acid digested 1a, 1,2-bis(4-pyridyl)hydrazine (bphy). m/z = 187.2 (M+H + ). 4
Figure S4. Coordination environments of each independent Zn 2+ in 1a (left: Zn1, Zn2, Zn3, Zn4) and 1b (right: Zn1, Zn2). Symmetry codes: a, x-0.5, y+0.5, z; b, -x+2.25, y+0.25, z+0.25; c, x, y+0.5, z+0.5; d, -x+1.25, y+0.25, z+0.25; e, x-0.5, y, z+0.5 (1a). a, x, -y+2.5, -z+1.5; b, x, -y+1.5, -z+1.5; c, x+0.5, y, -z+2; d, x+0.5, -y+1.5, z-0.5 (1b). Table S1. Zn-O and Zn-N bond lengths in 1a and 1b as shown in Figure S4. 1a (Fdd2) 1b (Pnna) Zn1 Zn2 Zn3 Zn4 Zn1 Zn2 Zn1-O15a 1.925(3) Zn2-O2 1.978(2) Zn3-O3 1.968(3) Zn4-O10 2.378(3) Zn1-O1 2.007(4) Zn2-O3c 2.149(6) Zn1-O16a 2.762(4) Zn2-O1 2.915(3) Zn3-O4 2.853(3) Zn4-O9 2.089(4) Zn1-O2 2.836(6) Zn2-O4c 2.345(9) Zn1-O12c 2.513(3) Zn2-O7e 2.187(3) Zn3-O5 2.672(3) Zn4-O13 1.954(3) Zn1-O1a 2.007(4) Zn2-O3d 2.149(6) Zn1-O11c 2.027(3) Zn2-O8e 2.299(4) Zn3-O6 2.009(4) Zn4-O14 2.870(3) Zn1-O2a 2.836(6) Zn2-O4d 2.345(9) Zn1-N16b 2.007(3) Zn2-N8d 2.004(3) Zn3-N5 2.073(3) Zn4-N12 2.020(3) Zn1-N1 2.022(5) Zn2-N4 2.031(5) Zn1-N4 2.046(3) Zn2-N1 2.020(3) Zn3-N9 2.032(4) Zn4-N13 2.019(3) Zn1-N1a 2.022(5) Zn2-N4b 2.031(5) 5
Figure S5. Conformations of bphy ligands in 1a ((1), (2), (3), (4)) and 1b ((1)). Table S2. N-N bond lengths and C-N-N-C torsion angles in 1a and 1b as shown in Figure S5. 1a (Fdd2) 1b (Pnna) (1) (2) (3) (4) (1) N2-N3 1.431(5) N6-N7 1.365(5) N10-N11 1.440(5) N14-N15 1.424(6) N2-N3 1.386(8) C8-N2-N3-C3 100.8(5) C29-N6-N7-C32 89.6(5) C39-N10-N11-C42 89.3(5) C49-N14-N15-C52 96.2(6) C11-N2-N3-C14 98.7(7) 6
Figure S6. Coordination environments of Zn 2+ for 2a (left: Zn1/Zn2, Zn3/Zn4) and 2b (right: Zn1/Zn2). Symmetry codes: a, x+1, y, z; b, x, y+1, z; c, x, y, z-1; d, x, y-1, z-1 (2a). a, x-1, y, z; b, x, y, z+1; c, x, y-1, z (2b). Table S3. Zn-O and Zn-N bond lengths in 2a and 2b as shown in Figure S6. 2a (P-1) 2b (P-1) Zn1/Zn2 Zn3/Zn4 Zn1/Zn2 Zn1-O1 2.051(4) Zn2-O2 2.024(4) Zn3-O11 2.013(4) Zn4-O12 2.019(4) Zn1-O4 2.014(2) Zn2-O3 2.033(2) Zn1-O5 2.008(4) Zn2-O6 2.047(4) Zn3-O13 2.010(4) Zn4-O14 2.061(4) Zn1-O8c 2.060(2) Zn2-O7c 2.030(2) Zn1-O8a 2.009(4) Zn2-O7a 2.058(4) Zn3-O3d 2.047(4) Zn4-O4d 2.031(4) Zn1-O6 2.056(2) Zn2-O5 2.024(2) Zn1-O9 2.047(4) Zn2-O10 2.007(4) Zn3-O15a 2.031(4) Zn4-O16a 2.033(4) Zn1-O2a 2.018(2) Zn2-O1a 2.040(2) Zn1-N8b 2.011(4) Zn2-N1 2.008(4) Zn3-N4c 2.015(4) Zn4-N5 1.993(4) Zn1-N2b 2.018(3) Zn2-N1 2.013(3) 7
Figure S7. Conformations of bphy ligands in 2a ((1), (2)) and 2b ((1)). Table S4. N-N bond lengths and C-N-N-C torsion angles in 2a and 2b as shown in Figure S7. 2a (P-1) 2b (P-1) (1) (2) (1) N2-N3 1.371(6) N6-N7 1.375(8) N3A-N4A 1.419(16) N3B-N4B 1.364(14) C27-N2-N3-C30 149.4(6) C45-N6-N7-C48 142.9(7) C17-N3A-N4A-C3A 142.0(13) C17-N3B-N4B-C3B 144.5(14) (h) (g) (f) (e) (d) (c) (b) (a) 5 10 15 20 25 30 2θ / deg Figure S8. PXRD patterns for (a) simulated 1a, (b) as-synthesized 1a, (c) simulated 1b, (d) as-synthesized 1b, (e) simulated 2a, (f) as-synthesized 2a, (g) simulated 2b, and (h) as-synthesized 2b. 8
100 90 80 1a 1b 2a 2b M / % 70 60 50 40 30 20 0 100 200 300 400 500 600 T / o C Figure S9. TG curves of 1a, 1b, 2a and 2b. (f) (e) (d) (c) (b) (a) 5 10 15 20 25 30 2θ / deg Figure S10. PXRD patterns for (a) simulated 1a, (b) simulated 1b, (c) 1 obtained by 1a activated at 200 o C, (d) 1 adsorbed DMF, (e) 1 obtained by 1b activated at 150 o C and (f) 1 adsorbed EtOH. 9
(f) (e) (d) (c) (b) (a) 5 10 15 20 25 30 2θ / deg Figure S11. PXRD patterns for (a) simulated 2a, (b) simulated 2b, (c) 2 obtained by 2a activated at 110 o C, (d) 2 adsorbed EtOH, (e) 2 obtained by 2b activated at 200 o C and (f) 2 adsorbed DMA. (b) (a) 5 10 15 20 25 30 2θ / deg Figure S12. PXRD patterns for 2 (a) before adsorption and (b) after desorption. 10