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Caption : fig. s1. the types of 5-connected h5l1 ligands and 6-connected h5l2 ligands with different dihedral angles in (a) 1, (b) 2, (c) 3, (d) 4. (znii(1), blue; znii(2), turquoise; cdii(1), green; cdii(2) teal; c, gray; o, red; h, white).

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Caption : fig. s2. zn-o bonds in compound 1 (a), cd-o bonds in compound 2 (b), zn-o bonds in compound 3 (c), cd-o bonds in compound 4 (d). (znii(1), blue; znii(2), turquoise; cdii(1), green; cdii(2) teal; c, gray; o, red; n, light blue; h, white).

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Caption : fig. s3. (a) local coordination environments of the znii ions in 1. (b) 1d chain with distorted mos in 1 along the c axis. (c) 1d tube in 1. (four coordinated znii(1) ions are marked as blue; six coordinated znii(2) ions are marked as turquoise ; c, gray; o, red. all hydrogen atoms and coordinated h2o are omitted for clarity).

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Caption : fig. s4. (a) 1d chain in 2 along the c axis, 3d framework structure and 1d tube in 2. (b) illustration of topology of 2: simplification of the inorganic clusters (5-connected node, teal), and the organic h5l1 linker (5-connected nodes, violet), leading to the (5,5)-connected binodal {47•63} topology. (seven coordinated cdii(1) ions are marked as green; six coordinated cdii(2) ions are marked as teal ; c, gray; o, red. all hydrogen atoms are omitted for clarity).

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Caption : fig. s5. (a) local coordination environments of the znii ions in 3. (b) 1d chain with sbus in 3 along the c axis. (four coordinated znii(1) ions are marked as blue; six coordinated znii(2) ions are marked as turquoise; c, gray; o, red. all hydrogen atoms and (ch3)2nh2+ are omitted for clarity).

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Caption : fig. s6. (a) local coordination environments of the cdii ions in 4. (b) 1d chain with distorted mos in 4 along the c axis. (four coordinated cdii(1) ions are marked as green; six coordinated cdii(2) ions are marked as teal; c, gray; o, red. all hydrogen atoms and (ch3)2nh2+ are omitted for clarity).

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Caption : fig. s7. infrared spectra for (a) 1, (b) 2, (c) 3, (d) 4. (kbr, cm-1)

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Caption : fig. s8. simulated (black), experimental (red), after recovery through centrifugation and washing with dmf (green) and after immersed in fe3+ ions solution with 1.1 mm concentration (blue) powder x-ray diffraction (pxrd) patterns for (a) 1, (b) 2, (c) 3, (d) 4.

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Caption : fig. s9. thermogravimetric analysis curves for (a) 1, (b) 2, (c) 3, (d) 4.

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Caption : fig. s10. fluorescent emission spectra of (a) ligand h5l1 (black), 1 (red); (b) ligand h5l1 (black), 2 (red); (c) ligand h5l2 (black), 3 (red); (d) ligand h5l2 (black), 4 (red) in solid state at room temperature.

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Caption : fig. s11. particle size distribution of compounds 1–4 by dls measurement. (the average size of compounds 1–4 after dispersing in dmf solvent are 6.1, 6.7, 6.5 and 6.3 μm in diameter, respectively)

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Caption : fig. s12. the color change of the luminescent responses for sensing the different metal ions (m = na+, k+, li+, ag+, mg2+, ca2+, pb2+, co2+, ni2+, cu2+, cd2+, zn2+, al3+, fe3+) in dmf solution for (a) 1, (b) 2, (c) 3, (d) 4 by the ultraviolet light.

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Caption : fig. s13. fluorescent emission spectra of original (red), after recovery through centrifugation and washing with dmf (green) and after immersed in fe3+ ions solution with 1.1 mm concentration (blue) for (a) 1, (b) 2, (c) 3, (d) 4.