Supporting information Study of Proton conductivity of a 2D flexible MOF and a 1D coordination polymer at higher temperature Suresh Sanda, Soumava Biswas and Sanjit Konar* Department of Chemistry, IISER Bhopal, Bhopal-462066, India. Fax: +91-755-669-2392; Tel: +91-755-6692339; E-mail: skonar@iiserb.ac.in Figure S1: Hydrogen bonding connectivity between the pyromellitate oxygen atoms and lattice water molecules (which are in between the layers) in compound 1. (Zn atoms and aldrithiol ligands are omitted for clarity). Colour code: C (grey), O (red).
Figure S2: Hydrogen bonding connectivity between pyromellitate oxygen atoms and lattice water molecules in compound 2. (Zn atoms and 4-pyridinethiolate ligands are omitted for clarity). Colour code: same as in fig. S1.
Figure S3: Hydrogen bonding network found in compound 1. Colour code: carbon (half grey), oxygen (red), nitrogen (blue), zinc (green). Sulphur (yellow). Hydrogen bonding connectivity (magenta). Figure S4: Hydrogen bonding network found in compound 2. Colour code: same as figure S3.
Figure S5: Water adsorption isotherm of compound 1. Figure S6: Water adsorption isotherm of compound 2.
Figure S7: PXRD patterns of compound 1. Simulated (black), Assynthesized (red). Table S1: Indexing result from the powder data of as-synthesized compound 1 collected at 25 deg From TREOR programme TRICLINIC P *** CONVENTIONAL CELL (METRIC SYMMETRY) * *** REDUCED-CELL *** A = 10.81715 ALFA = 107.3185 A = 9.03191 ALFA = 91.4017 B = 11.54403 BETA = 105.5810 B = 10.81715 BETA = 107.3185 C = 9.03191 GAMMA = 91.4017 C = 11.54403 GAMMA = 105.5810 VOLUME OF THE CONVENTIONAL CELL = 1030.44 A3 VOLUME OF THE REDUCED CELL = 1030.44 A3 H K L SST-OBS SST-CALC DELTA 2TH-OBS 2TH-CALC D-OBS FREE PARAM. 0 0 1 0.004943 0.004949-0.000006 8.063 8.068 10.9565 15 0 1 0 0.005579 0.005536 0.000043 8.567 8.534 10.3123 76 1 0 0 0.008703 0.008708-0.000005 10.706 10.709 8.2567 5 0 1 1 0.009347 0.009297 0.000050 11.096 11.066 7.9674 100 1 0 1 0.009523 0.009509 0.000015 11.201 11.192 7.8932 89-1 1 0 0.010127 0.010230-0.000104 11.551 11.610 7.6545 16 0-1 1 0.011681 0.011674 0.000007 12.409 12.406 7.1270 13-1 0 1 0.017806 15.337 1 1 1 0.017950 0.017871 0.000079 15.399 15.365 5.7493 29-1 1 1 0.018139 15.480 1 1 0 0.018374 0.018259 0.000115 15.581 15.532 5.6826 16 0 0 2 0.019770 0.019796-0.000026 16.166 16.177 5.4782 5-1 2 0 0.022825 17.379 0 1 2 0.022984 0.022955 0.000029 17.440 17.429 5.0808 44 0-1 2 0.027648 0.027710-0.000061 19.143 19.164 4.6325 10-1 -1 1 0.028548 0.028545 0.000003 19.455 19.454 4.5589 13 2 0 1 0.031450 0.031485-0.000035 20.430 20.442 4.3435 23 2-1 2 0.037921 22.458 2 0 2 0.038094 0.038036 0.000058 22.510 22.493 3.9466 17 1 2 0 0.038883 22.745 1-2 2 0.039055 0.039080-0.000025 22.796 22.803 3.8977 7 2 1 1 0.043940 0.043862 0.000078 24.200 24.178 3.6747 12 1-1 3 0.045866 0.045892-0.000026 24.733 24.740 3.5967 73 0-2 2 0.046724 0.046697 0.000028 24.967 24.959 3.5635 33 1 1 3 0.046789 24.984-1 -2 1 0.050282 0.050358-0.000076 25.916 25.936 3.4351 14 0.050381 25.942 3.4317 16 0 3 1 0.051278 0.051211 0.000068 26.176 26.158 3.4016 51 2-1 3 0.055563 0.055558 0.000006 27.268 27.267 3.2678 5 0-3 1 0.058457 0.058343 0.000113 27.983 27.955 3.1859 5 0 2 3 0.059579 0.059554 0.000025 28.256 28.250 3.1557 8 0.059902 28.334 3.1472 6 1-2 3 0.062019 0.062054-0.000035 28.841 28.849 3.0930 31 2 2 1 0.067311 30.074-1 3 2 0.067547 0.067453 0.000093 30.128 30.107 2.9638 5 2-2 3 0.067718 0.067705 0.000013 30.167 30.164 2.9600 5 1 3 1 0.067813 30.189 2-3 2 0.070910 30.887-2 0 2 0.071223 30.957 1 0 4 0.071295 0.071299-0.000004 30.973 30.974 2.8848 8 3-2 1 0.071316 30.978 2 2 2 0.071484 31.015 1 1 4 0.075736 0.076094-0.000359 31.948 32.026 2.7990 7 3-2 2 0.076096 0.076095 0.000001 32.026 32.026 2.7923 5-3 2 0 0.076434 32.099 1-3 3 0.089271 0.089288-0.000017 34.769 34.772 2.5781 6 0-1 4 0.089476 34.810 2 1 4 0.089640 34.843 NUMBER OF OBS. LINES = 33 NUMBER OF CALC. LINES = 46
Figure S8: PXRD patterns of compound 2. Simulated (black), Assynthesized (red). Table S2: Indexing result from the powder data of as-synthesized compound 2 collected at 25 deg From TREOR programme TRICLINIC P *** CONVENTIONAL CELL (METRIC SYMMETRY) *** *** REDUCED-CELL *** A = 9.36824 ALFA = 99.6692 A = 7.30548 ALFA = 90.8645 B = 14.13010 BETA = 111.9787 B = 9.36824 BETA = 99.6692 C = 7.30548 GAMMA = 90.8645 C = 14.13010 GAMMA = 111.9787 VOLUME OF THE CONVENTIONAL CELL = 873.57 A3 VOLUME OF THE REDUCED CELL = 873.57 A3 H K L SST-OBS SST-CALC DELTA 2TH-OBS 2TH-CALC D-OBS FREE PARAM. 1 1 0 0.007782 0.007768 0.000014 10.122 10.113 8.7317 8-1 1 0 0.010223 0.010205 0.000018 11.606 11.596 7.6185 15 0 2 0 0.012249 0.012256-0.000008 12.708 12.712 6.9599 100 0 2 1 0.013095 0.013089 0.000006 13.142 13.139 6.7312 5 1 0 1 0.013108 13.149-1 -2 1 0.014760 0.014759 0.000001 13.956 13.956 6.3403 9 1 2 0 0.015742 14.415-2 0 3 0.015752 14.420-2 -1 2 0.015857 0.015847 0.000010 14.468 14.464 6.1170 7 1-1 1 0.018167 0.018147 0.000020 15.492 15.484 5.7149 16-1 -2 2 0.018466 15.620 0 2 2 0.018598 0.018612-0.000014 15.676 15.682 5.6483 10-2 -1 3 0.018648 15.697-1 2 0 0.020599 0.020616-0.000017 16.503 16.510 5.3670 15 0 1 3 0.021921 0.021902 0.000018 17.029 17.021 5.2026 11-2 0 4 0.022529 0.022488 0.000041 17.265 17.249 5.1319 5-1 2 3 0.022663 17.317 0 3 0 0.027535 0.027577-0.000042 19.103 19.118 4.6420 13 0 3 1 0.027653 19.145-2 -2 3 0.027672 19.151 0 2 3 0.028786 0.028826-0.000040 19.536 19.550 4.5401 7-1 -1 4 0.028954 19.594-2 2 4 0.033561 0.033568-0.000007 21.112 21.114 4.2046 6 0.036682 22.084 4.0218 6-1 3 3 0.036941 0.036934 0.000008 22.163 22.160 4.0077 7 1 1 3 0.041112 0.041128-0.000016 23.397 23.402 3.7990 19-2 2 5 0.043510 0.043481 0.000029 24.080 24.071 3.6928 11 0-1 4 0.043613 24.108-2 -2 5 0.048858 25.540-2 3 1 0.048995 0.048972 0.000022 25.576 25.570 3.4800 11 0 4 0 0.049026 25.585 0.051448 25.740 3.3960 60 0.052455 26.220 3.3632 9 0.055491 26.480 3.2699 9 0.056092 27.250 3.2524 5 0.058240 27.400 3.1918 23 0.064393 27.930 3.0355 14 0.064908 29.520 3.0234 6 0-2 3 0.065641 0.065595 0.000046 29.690 29.679 3.0065 9-1 0 4 0.065840 29.736-1 1 2 0.066005 29.774 1-3 5 0.066900 0.067032-0.000132 29.980 30.010 2.9781 12 1-2 6 0.071866 0.071772 0.000095 31.100 31.079 2.8733 8 0 3 0 0.072771 0.072790-0.000019 31.300 31.304 2.8554 6 NUMBER OF OBS. LINES = 30 NUMBER OF CALC. LINES = 36
Figure S9: VT-PXRD of compound 1 in the range of 25-85 C. Table S3: Indexing result from the powder data of as-synthesized compound 1 collected at 85 deg From TREOR programme TRICLINIC P *** CONVENTIONAL CELL (METRIC SYMMETRY) *** *** REDUCED-CELL *** A = 10.82034 ALFA = 107.1589 A = 9.04703 ALFA = 91.4142 B = 11.54461 BETA = 105.8315 B = 10.82034 BETA = 107.1589 C = 9.04703 GAMMA = 91.4142 C = 11.54461 GAMMA = 105.8315 VOLUME OF THE CONVENTIONAL CELL = 1032.04 A3 VOLUME OF THE REDUCED CELL = 1032.04 A3 H K L SST-OBS SST-CALC DELTA 2TH-OBS 2TH-CALC D-OBS FREE PARAM. 0 0 1 0.004943 0.004941 0.000002 8.063 8.061 10.9565 15 0 1 1 0.005579 0.005548 0.000032 8.567 8.543 10.3123 77 0 1 0 0.009347 0.009291 0.000056 11.096 11.063 7.9674 100 1 0 0 0.009523 0.009517 0.000006 11.201 11.197 7.8932 89 1 1 0 0.010127 0.010164-0.000037 11.551 11.572 7.6545 16 0 1 2 0.011681 0.011687-0.000006 12.409 12.412 7.1270 13-1 1 1 0.017950 0.017938 0.000012 15.399 15.394 5.7493 29-1 -1 1 0.018018 15.428-1 1 2 0.018374 0.018306 0.000068 15.581 15.552 5.6826 16 0 0 2 0.019770 0.019764 0.000007 16.166 16.163 5.4782 5 0-1 1 0.022984 0.022916 0.000069 17.440 17.414 5.0808 44-1 1 0 0.027452 19.074 0 1 3 0.027648 0.027707-0.000059 19.143 19.164 4.6325 10-1 1 3 0.028548 0.028556-0.000008 19.455 19.458 4.5589 14-2 0 1 0.031450 0.031468-0.000017 20.430 20.436 4.3435 23 2 0 0 0.038094 0.038068 0.000025 22.510 22.502 3.9466 17-1 2 3 0.039021 22.786 1 2 3 0.039055 0.039069-0.000014 22.796 22.800 3.8977 7-2 1 2 0.043940 0.043960-0.000020 24.200 24.206 3.6747 12-2 -1 2 0.044119 24.250-1 2 1 0.045771 24.707 1 1 3 0.045866 0.045893-0.000026 24.733 24.740 3.5967 73-1 -2 1 0.045930 24.750 0 2 4 0.046724 0.046747-0.000023 24.967 24.973 3.5635 32 1-1 1 0.046848 25.000-1 2 4 0.050282 0.050469-0.000187 25.916 25.965 3.4351 14 0.050381 25.942 3.4317 16 0 3 2 0.051278 0.051278 0.000000 26.176 26.176 3.4016 51-2 -2 1 0.051422 26.213 2 1 2 0.055563 0.055550 0.000014 27.268 27.265 3.2678 5 0 3 4 0.058457 0.058466-0.000009 27.983 27.985 3.1859 5 0-2 1 0.059579 0.059472 0.000107 28.256 28.230 3.1557 8 2 3 1 0.059902 0.060252-0.000350 28.334 28.418 3.1472 6 1 2 4 0.062019 0.062059-0.000040 28.841 28.850 3.0930 30 1 3 0 0.067202 30.049-2 2 3 0.067547 0.067549-0.000002 30.128 30.128 2.9638 5 2 2 3 0.067718 0.067644 0.000073 30.167 30.150 2.9600 5-1 3 3 0.068068 30.247 3 2 0 0.070952 30.896-2 0 4 0.070957 30.898 1 0 3 0.071295 0.071298-0.000003 30.973 30.974 2.8848 8-3 -1 2 0.071519 31.023 3 2 1 0.075736 0.075837-0.000102 31.948 31.970 2.7990 7-3 -2 1 0.075948 31.994 1-1 2 0.076096 0.076125-0.000029 32.026 32.032 2.7923 5
-2-3 1 0.089271 0.089272-0.000001 34.769 34.769 2.5781 6 1 3 5 0.089321 34.779 0 1 5 0.089395 34.794 NUMBER OF OBS. LINES = 32 NUMBER OF CALC. LINES = 47 Figure S10: VT-PXRD of compound 2 in the range of 25-85 C. Table S4: Indexing result from the powder data of as-synthesized compound 2 collected at 85 deg From TREOR programme TRICLINIC P *** CONVENTIONAL CELL (METRIC SYMMETRY) *** *** REDUCED-CELL *** A = 9.34582 ALFA = 99.5692 A = 7.34054 ALFA = 90.9645 B = 14.15600 BETA = 112.1787 B = 9.34582 BETA = 99.5692 C = 7.34054 GAMMA = 90.9645 C = 14.15600 GAMMA = 112.1787 VOLUME OF THE CONVENTIONAL CELL = 870.34 A3 VOLUME OF THE REDUCED CELL = 870.34 A3 H K L SST-OBS SST-CALC DELTA 2TH-OBS 2TH-CALC D-OBS FREE PARAM. 1 0 1 0.007782 0.007731 0.000051 10.122 10.088 8.7317 8-1 0 1 0.010223 0.010274-0.000051 11.606 11.635 7.6185 15 0 0 2 0.012249 0.012260-0.000012 12.708 12.714 6.9599 100 1 1 2 0.013095 0.013085 0.000010 13.142 13.137 6.7312 6 2 1 1 0.014760 0.014734 0.000025 13.956 13.944 6.3403 9 2 2 1 0.015771 14.429 2 2 0 0.015857 0.015842 0.000015 14.468 14.461 6.1170 7 0-1 2 0.018167 0.018140 0.000027 15.492 15.481 5.7149 16-1 1 0 0.018598 0.018487 0.000111 15.676 15.629 5.6483 10-2 -1 1 0.020413 16.428 1-1 1 0.020599 0.020577 0.000022 16.503 16.495 5.3670 15-1 0 2 0.020741 16.561 2 2 2 0.021921 0.021831 0.000090 17.029 16.994 5.2026 11-2 -2 1 0.022042 17.076-1 1 1 0.022529 0.022527 0.000001 17.265 17.264 5.1319 6 2 3 1 0.027381 19.049 0 0 3 0.027535 0.027586-0.000051 19.103 19.121 4.6420 13 1-1 2 0.028786 0.028797-0.000011 19.536 19.540 4.5401 7 2 1 3 0.033561 0.033577-0.000015 21.112 21.117 4.2046 6-1 -3 1 0.036941 0.036952-0.000011 22.163 22.166 4.0077 7-2 0 2 0.041112 0.041095 0.000017 23.397 23.392 3.7990 19-2 1 0 0.043510 0.043562-0.000052 24.080 24.094 3.6928 11 2 0 3 0.043706 24.134-2 1 1 0.048874 25.544-1 1 3 0.048995 0.048999-0.000004 25.576 25.577 3.4800 11 0 0 4 0.049042 25.589 0.051448 25.740 3.3960 60 0.052455 26.220 3.3632 9 0.055491 26.480 3.2699 9 0.056092 27.250 3.2524 5 0.058240 27.400 3.1918 23 0.064393 29.400 3.0355 14 0-2 3 0.065641 0.065595 0.000046 29.690 29.679 3.0065 9-1 0 4 0.065840 29.736-1 1 2 0.066005 29.774 1 0 3 0.066900 0.066932-0.000032 29.980 29.987 2.9781 12 1-2 6 0.071866 0.071772 0.000095 31.100 31.079 2.8733 8 0 3 0 0.072771 0.072790-0.000019 31.300 31.304 2.8554 6 NUMBER OF OBS. LINES = 22 NUMBER OF CALC. LINES = 38
Figure S11: PXRD patterns of as-synthesized (red) and humidified samples (at 80 C and 95% RH for 12 hours) of compound 1 (blue). Table S5: Indexing result from the powder data of humidified compound 1 at 80 deg, 95% RH. From TREOR programme TRICLINIC P *** CONVENTIONAL CELL (METRIC SYMMETRY) *** *** REDUCED-CELL *** A = 10.86839 ALFA = 107.1109 A = 9.05886 ALFA = 92.1968 B = 11.60474 BETA = 104.9110 B = 10.86839 BETA = 107.1109 C = 9.05886 GAMMA = 92.1968 C = 11.60474 GAMMA = 104.9110 VOLUME OF THE CONVENTIONAL CELL = 1047.13 A3 VOLUME OF THE REDUCED CELL = 1047.13 A3 H K L SST-OBS SST-CALC DELTA 2TH-OBS 2TH-CALC D-OBS FREE PARAM. 0 0 1 0.004908 0.004898 0.000010 8.035 8.026 10.9947 26 0 1 0 0.005463 0.005463 0.000001 8.478 8.477 10.4212 100 0 1 1 0.009080 0.009083-0.000003 10.936 10.938 8.0834 93 1 0 0 0.009420 0.009407 0.000013 11.139 11.132 7.9364 78 1 1 1 0.010176 0.010204-0.000027 11.580 11.595 7.6357 12 0-1 1 0.011626 0.011638-0.000012 12.380 12.386 7.1440 18 0.016786 14.888 5.9453 18 1 1 2 0.017911 15.382 1-1 1 0.017953 0.017912 0.000041 15.400 15.383 5.7488 31 0 0 2 0.019633 0.019592 0.000041 16.109 16.092 5.4973 6 0 2 0 0.021854 0.021850 0.000004 17.002 17.001 5.2106 5 0 1 2 0.022500 17.254 1 2 1 0.022631 0.022737-0.000106 17.304 17.345 5.1203 43 0-1 2 0.027610 0.027610 0.000000 19.129 19.129 4.6357 8 1-1 2 0.028176 0.028174 0.000002 19.326 19.326 4.5889 13 2 0 1 0.031089 0.031106-0.000017 20.311 20.317 4.3686 19 2 0 0 0.037680 0.037627 0.000053 22.386 22.370 3.9682 18 0 1 3 0.045713 24.691-1 -1 2 0.045830 0.045859-0.000029 24.723 24.731 3.5981 79-1 1 2 0.045902 24.743 0-2 2 0.046503 0.046552-0.000049 24.907 24.920 3.5720 46 1-2 2 0.049690 0.049693-0.000004 25.760 25.761 3.4555 13 2 2 3 0.051331 26.190 1 3 2 0.051548 0.051348 0.000201 26.246 26.194 3.3927 34-2 -1 1 0.055520 0.055530-0.000011 27.257 27.260 3.2691 6 0.058710 28.045 3.1790 8 2-1 3 0.061901 28.813-1 -2 2 0.062150 0.062224-0.000074 28.872 28.890 3.0898 39-1 2 2 0.062312 28.910-2 1 1 0.063261 0.063283-0.000021 29.135 29.140 3.0625 8-1 0 3 0.070618 30.822 1-2 3 0.071000 0.071029-0.000029 30.907 30.914 2.8908 8 2 3 0 0.071329 30.981 0-3 2 0.076449 0.076419 0.000030 32.102 32.096 2.7859 6 0.076571 32.102 2.7837 6 NUMBER OF OBS. LINES = 26 NUMBER OF CALC. LINES = 32
Figure S12: PXRD patterns of as-synthesized (red) and humidified samples (at 80 C and 95% RH for 12 hours) of compound 2 (blue). Table S6: Indexing result from the powder data of humidified compound 2 at 80 deg, 95% RH. From TREOR programme TRICLINIC P *** CONVENTIONAL CELL (METRIC SYMMETRY) *** *** REDUCED-CELL *** A = 9.01424 ALFA = 99.0660 A = 7.37569 ALFA = 90.6445 B = 14.21562 BETA = 112.9280 B = 9.01424 BETA = 99.0660 C = 7.37569 GAMMA = 90.6445 C = 14.21562 GAMMA = 112.9280 VOLUME OF THE CONVENTIONAL CELL = 886.83 A3 VOLUME OF THE REDUCED CELL = 886.83 A3 H K L SST-OBS SST-CALC DELTA 2TH-OBS 2TH-CALC D-OBS FREE PARAM. 0 1 1 0.010301 0.010299 0.000001 11.650 11.649 7.5896 10 0 0 2 0.012286 0.012278 0.000008 12.728 12.724 6.9494 100 0-1 1 0.015914 0.015922-0.000008 14.494 14.498 6.1060 5-1 1 2 0.018228 0.018224 0.000004 15.519 15.517 5.7053 10 1 1 0 0.018290 0.018246 0.000043 15.545 15.526 5.6957 9-1 -1 2 0.018536 0.018535 0.000001 15.650 15.650 5.6577 6 0.018598 15.676 5.6483 6-1 1 1 0.020631 0.020633-0.000002 16.517 16.517 5.3628 9-1 1 3 0.021954 0.021955 0.000000 17.042 17.042 5.1986 7-1 0 4 0.027561 19.113 0 0 3 0.027610 0.027626-0.000016 19.129 19.135 4.6357 13 0 2 2 0.041203 0.041197 0.000006 23.423 23.421 3.7948 10-1 -1 4 0.043381 24.043 1 0 2 0.043557 0.043563-0.000006 24.093 24.094 3.6908 6-1 2 3 0.049111 25.607 0 0 4 0.049113 25.608 1 2 1 0.049143 0.049155-0.000012 25.616 25.619 3.4747 7 0 2 3 0.050917 0.050922-0.000005 26.082 26.083 3.4136 10-1 2 1 0.053414 0.053412 0.000001 26.725 26.725 3.3329 10 0.056092 27.400 3.2524 5 0.058240 27.930 3.1918 23 0.064393 29.400 3.0355 14 0.064908 29.520 3.0234 6 0-2 3 0.065641 0.065595 0.000046 29.690 29.679 3.0065 9 1 0 4 0.065840 29.736-1 1 2 0.066005 29.774 1-3 5 0.066900 0.067036-0.000136 29.980 30.011 2.9781 12 1-2 6 0.071866 0.071773 0.000094 31.100 31.079 2.8733 8 1 1 4 0.072703 31.285 0 3 0 0.072771 0.072793-0.000022 31.300 31.305 2.8554 6 0 3 1 0.073068 31.365 NUMBER OF OBS. LINES = 23 NUMBER OF CALC. LINES = 26
Figure S13: DSC plot of compound 1 showing an endothermic peak at ~120 C correspond to phase change. Figure S14: DSC plot of compound 2 showing an endothermic peak at ~120 C correspond to phase change.
Figure S15: PXRD patterns of compound 1. As synthesized (red), After immersion in water for 24 hours (green). Table S7: Indexing result from the powder data of compound 1 immersed in H 2 O From TREOR programme TRICLINIC P *** CONVENTIONAL CELL (METRIC SYMMETRY) *** *** REDUCED-CELL *** A = 10.85447 ALFA = 107.0554 A = 9.06896 ALFA = 91.7135 B = 11.55646 BETA = 105.3191 B = 10.85447 BETA = 107.0554 C = 9.06896 GAMMA = 91.7135 C = 11.55646 GAMMA = 105.3191 VOLUME OF THE CONVENTIONAL CELL = 1041.79 A3 VOLUME OF THE REDUCED CELL = 1041.79 A3 H K L SST-OBS SST-CALC DELTA 2TH-OBS 2TH-CALC D-OBS FREE PARAM. 0 0 1 0.004932 0.004928 0.000005 8.054 8.051 10.9680 22 0 1 0 0.005488 0.005488 0.000000 8.497 8.497 10.3979 100 0 1 1 0.009168 0.009205-0.000037 10.989 11.011 8.0449 68-1 0 1 0.009442 0.009456-0.000014 11.152 11.161 7.9273 56 1 1 0 0.010176 0.010159 0.000018 11.580 11.570 7.6357 9 0-1 1 0.011626 0.011627-0.000002 12.380 12.381 7.1440 7 1 0 1 0.017560 0.017589-0.000029 15.230 15.242 5.8128 7-1 1 1 0.017656 15.272 1 1 1 0.017953 0.017942 0.000012 15.400 15.395 5.7488 24-1 1 0 0.018006 15.423 0 0 2 0.019729 0.019711 0.000018 16.149 16.141 5.4840 5 1 2 0 0.022733 0.022700 0.000033 17.344 17.331 5.1088 31 0 1 2 0.022776 17.360 1-1 1 0.028214 0.028212 0.000002 19.340 19.339 4.5858 8-2 0 1 0.031169 0.031172-0.000003 20.337 20.339 4.3630 13-2 0 2 0.037767 0.037823-0.000056 22.412 22.429 3.9636 12-2 -1 2 0.037886 22.448-1 2 0 0.038425 0.038395 0.000030 22.609 22.600 3.9295 6 1 2 2 0.045698 24.687-1 -1 3 0.045830 0.045943-0.000114 24.723 24.754 3.5981 52 0-2 2 0.046503 0.046509-0.000007 24.907 24.909 3.5720 25-1 1 3 0.046522 24.912 0 3 0 0.049391 0.049395-0.000003 25.681 25.682 3.4660 6 1-2 1 0.049789 0.049812-0.000022 25.787 25.792 3.4521 10 0 3 1 0.050690 0.050688 0.000002 26.023 26.022 3.4213 9-1 -3 1 0.050713 26.029 2 2 1 0.051274 26.175 1 3 1 0.051447 0.051578-0.000131 26.220 26.254 3.3960 30 0-3 1 0.057958 0.057956 0.000002 27.861 27.861 3.1996 5 0 2 3 0.059034 0.059034 0.000000 28.124 28.124 3.1703 7 0 3 2 0.061837 28.798 2-1 1 0.061985 28.833-1 -2 3 0.062095 0.062119-0.000024 28.859 28.865 3.0912 26 1 1 3 0.063074 29.091-1 2 3 0.063206 0.063277-0.000071 29.122 29.138 3.0639 6-2 -3 2 0.070943 30.895 1-2 2 0.071118 0.071084 0.000034 30.934 30.926 2.8884 5-1 0 4 0.071172 30.946 NUMBER OF OBS. LINES = 25 NUMBER OF CALC. LINES = 38
Figure S16: PXRD patterns of compound 2. As synthesized (red), After immersion in water for 24 hours (green). Table S8: Indexing result from the powder data of compound 2 immersed in H 2 O From TREOR programme TRICLINIC P *** CONVENTIONAL CELL (METRIC SYMMETRY) *** *** REDUCED-CELL *** A = 9.34924 ALFA = 99.8690 A = 7.37962 ALFA = 91.9671 B = 14.32408 BETA = 111.9677 B = 9.34924 BETA = 99.8690 C = 7.37962 GAMMA = 91.9671 C = 14.32408 GAMMA = 111.9677 VOLUME OF THE CONVENTIONAL CELL= 878.64 A3 VOLUME OF THE REDUCED CELL= 878.64 A3 H K L SST-OBS SST-CALC DELTA 2TH-OBS 2TH-CALC D-OBS FREE PARAM 1 0 1 0.007782 0.007739 0.000043 10.122 10.094 8.7317 8-1 0 1 0.010223 0.010276-0.000053 11.606 11.636 7.6185 15 0 0 2 0.012249 0.012272-0.000023 12.708 12.720 6.9599 100 1 2 0 0.012442 12.808 1 1 2 0.013095 0.013075 0.000021 13.142 13.132 6.7312 5 2 1 1 0.014760 0.014710 0.000049 13.956 13.933 6.3403 9 1 0 2 0.015675 14.384 2 2 0 0.015857 0.015713 0.000143 14.468 14.402 6.1170 7 0-1 2 0.018167 0.018123 0.000044 15.492 15.473 5.7149 16-1 1 0 0.018598 0.018475 0.000123 15.676 15.624 5.6483 10 1-1 1 0.020599 0.020569 0.000030 16.503 16.491 5.3670 15-1 0 2 0.020748 16.564 2 2 2 0.021734 16.955-2 -2 1 0.021921 0.021907 0.000014 17.029 17.023 5.2026 11-1 1 1 0.022529 0.022517 0.000012 17.265 17.260 5.1319 5 2 3 0 0.027535 0.027478 0.000057 19.103 19.083 4.6420 13 0 0 3 0.027612 19.130 1-1 2 0.028786 0.028799-0.000013 19.536 19.541 4.5401 7 2 1 3 0.033561 0.033592-0.000030 21.112 21.122 4.2046 6 0-1 3 0.033757 21.174-1 -3 1 0.036682 0.036699-0.000017 22.084 22.089 4.0218 6 0.036941 22.163 4.0077 7-2 0 2 0.041112 0.041103 0.000008 23.397 23.394 3.7990 19-2 1 0 0.043510 0.043566-0.000056 24.080 24.095 3.6928 11-2 1 1 0.048877 25.545-1 1 3 0.048995 0.049009-0.000014 25.576 25.580 3.4800 11 0 0 4 0.049088 25.601 0.049613 25.740 3.4582 41 0.051448 26.220 3.3960 59 0.052455 26.480 3.3632 8 0.055491 27.250 3.2699 9 0.056092 27.400 3.2524 5 0.058240 27.930 3.1918 23 0.064393 29.400 3.0355 14 0.064908 29.520 3.0234 6 0 2 5 0.065641 0.065596 0.000045 29.690 29.679 3.0065 8 1 0 3 0.065841 29.736 1-3 5 0.066900 0.067032-0.000132 29.980 30.010 2.9781 12 1-2 6 0.071866 0.071772 0.000095 31.100 31.079 2.8733 8 1 1 4 0.072704 31.285 0 3 0 0.072771 0.072790-0.000019 31.300 31.304 2.8554 6 0 3 1 0.073065 31.365 NUMBER OF OBS. LINES = 31 NUMBER OF CALC. LINES = 33
Figure S17: Nyquist plots of compound 1 at 25 C, 30 C, 35 C and 95% RH. (For 303 K and 308 K the error bars are contained within the plot-shape) Figure S18: Nyquist plots of compound 1 at 76 C, 78 C, 80 C and 95% RH. (Error bars are contained within the plot-shape)
Figure S19: Nyquist plots of compound 2 at 25 C, 30 C, 35 C and 95% RH. Figure S20: Nyquist plots of compound 2 at 76 C, 78 C, 80 C and 95% RH.
Figure S21: TGA plots as-synthesized (black) and humidified (at 80 C and 95% RH) samples (red) of compound 1. Figure S22: TGA plots as-synthesized (black) and humidified (at 80 C and 95% RH) samples (red) of compound 2.
Figure S23: TGA plots as-synthesized (black) and dehydrated samples (green) of compound 1. Figure S24: TGA plots as-synthesized (black) and dehydrated samples (green) of compound 2.
Figure S25: IR spectrum of compound 1. D 2 O. (Broad peak at 2500 cm -1 which is due to O-D stretching frequency and confirms the D 2 O exchange) Figure S26: IR spectrum of compound 2. D 2 O. (Broad peak at 2500 cm -1 which is due to O-D stretching frequency and confirms the D 2 O exchange)
Figure S27: Nyquist plot of compound 1.D 2 O at 80 C, 95% RH. Figure S28: Nyquist plot of compound 2.D 2 O at 80 C, 95% RH.
Figure S29: Plausible water molecule accumulation inside the framework of compound 1. (Calculated through Monte Carlo simulations from Material Studio 6.1 program using sorption module) Figure S30: A view of water density distribution inside the framework of compound 1 (Calculated through Monte Carlo simulations from Material Studio 6.1 program using sorption module). (Bonding connectivity between the framework atoms is removed for clarity).
Figure S31: Plausible water accumulation inside the framework of compound 2. (Calculated through Monte Carlo simulations from Material Studio 6.1 program using sorption module). Figure S32: A view of water density distribution inside the framework of compound 2 (Calculated through Monte Carlo simulations from Material Studio 6.1 program using sorption module). (Bonding connectivity between the framework atoms is removed for clarity).
Figure S33: Nyquist plots of compound 1 at 25 C and 75%, 85%, 95% RH. Figure S34: Nyquist plots of compound 2 at 25 C and 75%, 85%, 95% RH.
Figure S35: Nyquist plot of dehydrated compound 1 at 25 C and 95% RH. Figure S36: Nyquist plot of dehydrated compound 2 at 25 C and 95% RH.
Figure S37: Relative humidity vs conductivity plot of dehydrated compound 1 at 25 C, adsorption isotherm of compound 1 in the range of P/P 0 = 0.4 to 1 bar (inset). Figure S38: Relative humidity vs conductivity plot of dehydrated compound 2 at 25 C, adsorption isotherm of compound 2 in the range of P/P 0 = 0.4 to 1 bar (inset).
Figure S39: Nyquist plots of compound 1 at 35%, 45% RH and 80 C. Figure S40: Nyquist plots of compound 1 at 85%, 95% RH and 80 C.
Figure S41: Nyquist plots of compound 2 at 35%, 45% RH and 80 C. Figure S42: Nyquist plots of compound 2 at 85%, 95% RH and 80 C.
Figure S43: Relative humidity vs conductivity plot of compound 1 at 80 C. Figure S44: Relative humidity vs conductivity plot of compound 2 at 80 C.
Figure S45: Nyquist plots of compound 1 at 25 C, 35 C and zero humidity. Figure S46: Nyquist plots of compound 1 at 75 C, 80 C and zero humidity.
Figure S47: Conductivity vs temperature plot of compound 1 under anhydrous conditions. Figure S48: The time-dependent proton conductivity experiments of compounds 1 in 3 different cycles at 80 C, 95% RH.
Figure S49: The time-dependent proton conductivity experiments of compounds 1 in 3 cycles at 80 C, 95% RH. Figure S50: PXRD patterns of compound 1. As synthesized sample (black), after time dependent conductivity measurement for 10 hours (pink).
Figure S51: PXRD patterns of compound 2. As synthesized sample (black), after time dependent conductivity measurement for 10 hours (pink).