SUPPLEMENTARY INFORMATION

Transcription

1 SUPPLEMENTARY INFORMATION Bridging-Ligand-Substitution Strategy for the Preparation of Metal-Organic Polyhedra Jian-Rong Li and Hong-Cai Zhou Department of Chemistry, Texas A&M University, College Station, TX , USA Fax: (+01) , 1. Materials and Methods Contents 2. Syntheses, Reactions, and Characterizations 3. Control Experiments on the One-Pot Reaction for the Synthesis of MOPs with Mixed Ligands 4. X-ray Crystallography (Single-crystal diffraction) 5. Absorption Spectra 6. Powder X-ray Diffraction (PXRD) 7. Thermogravimetric Analysis (TGA) 8. Gas Adsorption 9. References nature chemistry 1

2 supplementary information 1. Materials and Methods All the general reagents and solvents were commercially available and used as received. Organic ligands, 1,3-benzenedicarboxylic acid [H 2 (1,3-BDC), F1, the number of corresponding deprotonated form of this ligand was assigned as F, the same case for other ligands was used throughout this paper], 5-tert-butyl-1,3-benzenedicarboxylic acid [H 2 (5-tBu-1,3-BDC), A1], 5-hydroxy-1,3-benzenedicarboxylic acid [H 2 (5-OH-1,3-BDC), B1], 5-sulfo-1,3-benzenedicarboxylic acid monosodium salt [NaH 2 (5-SO 3-1,3-BDC), NaC1], and 4-nitrobenzenecarboxylic acid [H(4-NO 2 -BC), I1] were purchased from VWR. 2,7-Naphthalenedicarboxylic acid [H 2 (2,7-NDC), E1] was obtained by the hydrolyzation of dimethyl-2,7-naphthalenedicarboxylate, which was purchased from TCI America. 9H-3,6-Carbazoledicarboxylic acid [H 2 (9H-3,6-CDC) also abbreviated as H 2 CDC, H1] was prepared according to our published procedure 1. Other two organic ligands were newly synthesized as described below. 1 H NMR data were collected on a Mercury 300 spectrometer. The fast neutron activation analysis (FNAA) was used to determine the ratio of sodium and copper in 3 using 1 MW TRIGA research reactor located at Texas A&M University's Nuclear Science Center. FT-IR data were recorded on an IRAffinity-1 instrument. TGA data were obtained on a TGA-50 (SHIMADZU) thermogravimetric analyzer with a heating rate of 2 C min 1 under N 2 atmosphere. The powder X-ray diffraction patterns (PXRD) were recorded on a BRUKER D8-Focus Bragg-Brentano X-ray Powder Diffractometer equipped with a Cu sealed tube (λ = ) at room temperature. Simulation of the PXRD spectrum was carried out by the single-crystal data and diffraction-crystal module of the Mercury program available free of charge via internet at Le Bail patterns decomposition of the PXRD data was performed by using TOPAS software. 2. Syntheses, Reactions, and Characterizations 2.1. Ligand, 3,3 -(ethyne-1,2-diyl)dibenzoic acid [H 2 (3,3 -EDDB), D1] 2 nature chemistry

3 supplementary information (a) Ethyl-3-[(trimethylsilyl)ethynyl]benzoate Under nitrogen gas trimethylsilylacetylene (2.1 ml, 14.9 mmol) was added to a solution of ethyl-3-iodobenzoate (2.0 ml, 11.9 mmol) in deoxygenated distilled triethylamine (TEA, 30 ml) with tetrakis(triphenylphosphine)palladium(0) (345 mg, 0.30 mmol) and copper(i) iodide (23 mg, 0.12 mmol) in a 100 ml Schlenk flask at 0 o C. After stirring for 1 h at room temperature, the reaction system was heated to 70 o C; at this temperature the reaction solution was further stirred for 12 hours. The reaction system was cooled to room temperature and then a saturated aqueous solution of ammonium chloride was added. The aqueous solution was extracted three times with dichloromethane. The combined dichloromethane layer was washed with brine and dried over sodium sulfate. After evaporation of the dichloromethane, the crude residue was purified by column chromatography on silica gel with ethyl acetate/hexane (2%) as eluent to give pure ethyl-3-[(trimethylsilyl)ethynyl]benzoate as a white solid (2.3 g, 78% yield based on ethyl-3-iodobenzoate). 1 H NMR (300 MHz, CDCl 3 ): δ 0.26 (s, 9H), 1.39 (t, 3H), 4.38 (q, 2H), 7.37 (t, 1H), 7.62 (d, 1H), 7.98 (d, 1H), 8.13 (s, 1H). (b) Ethyl-3-(ethynyl)benzoate A solution of ethyl-3-[(trimethylsilyl)ethynyl]benzoate (2.3 g, 9.3 mmol) in dichloromethane (50 ml) was treated with 12 ml of n-bu 4 NF xh 2 O (12 mmol) in THF (1 mol/l in THF) at room temperature for 12 h. The reaction solution was washed with 50 ml of water and then was dried over sodium sulfate. After the solvent evaporated, the residue was purified by column chromatography on silica gel with ethyl acetate/hexane (2%) as eluent to give ethyl-3-(ethynyl)benzoate as a white solid (1.6 g, 98% yield). 1 H NMR (300 MHz, CDCl 3 ): 1.30 (t, 3H), 4.28 (q, 2H), 7.29 (t, 1H), 7.55 (d, 1H), 7.91 (d, 1H), 8.07 (s, 1H). (c) Diethyl-3,3 -(ethyne-1,2-diyl)dibenzoate nature chemistry 3

4 supplementary information Under nitrogen gas ethyl-3-iodobenzoate (1.5 ml, 9.2 mmol) was added to a solution of ethyl-3-(ethynyl)benzoate (1.6 g, 9.2 mmol) in deoxygenated distilled triethylamine (TEA, 30 ml) with tetrakis(triphenylphosphine)palladium(0) (236 mg, 0.20 mmol) and copper(i) iodide (19 mg, 0.10 mmol) in a 100 ml Schlenk flask at room temperature. After stirred at reflux temperature for 24 hours, the reaction system was cooled to room temperature, to which a saturated aqueous solution of ammonium chloride and dichloromethane were added. The organic layer was separated and the aqueous layer was further extracted three times with dichloromethane. The combined dichloromethane layer was washed with brine and dried over sodium sulfate. After evaporation of the dichloromethane, the crude residue was recrystallized from hexane to give pure diethyl-3,3 -(ethyne-1,2-diyl)dibenzoate as a white crystal solid (1.8 g, 60% yield). 1 H NMR (300 MHz, CDCl 3 ): 1.42 (t, 6H), 4.41 (q, 4H), 7.45 (t, 2H), 7.72 (d, 2H), 8.03 (d, 2H), 8.23 (s, 2H). (d) 3,3 -(Ethyne-1,2-diyl)dibenzoic acid [H 2 (3,3 -EDDB), D1] Diethyl-3,3 -(ethyne-1,2-diyl)dibenzoate (1.8 g) was dissolved in 30 ml of mixed solvent of THF and MeOH (v/v = 1:1), to which 15 ml of 2N NaOH aqueous solution was added. After the mixture stirred at 60 o C overnight, the organic phase was removed. The aqueous phase was filtrated and acidified with diluted hydrochloric acid to give white precipitate, which was filtered and washed with water to obtain pure 3,3 -(ethyne-1,2-diyl)dibenzoic acid (yield: 1.4 g, 95%). 1 H NMR (300 MHz, DMSO-d 6 ): 7.58 (t, 2H), 7.83 (d, 2H), 7.98 (d, 2H), 8.09 (s, 2H). FT-IR (neat, cm 1 ): 2877(w), 2671(w), 2545(w), 1911(w), 1680(s), 1606(m), 1579(m), 1485(w), 1452(m), 1410(m), 1322(m), 1288(s), 1259(m), 1164(m), 1117(w), 1085(w), 914(s), 819(m), 777(m), 752(s), 678(s) Ligand, 3,3 -(2-amino-5-iso-propyl-1,3-phenylene)bis(ethyne-2,1-diyl)dibenzoic acid [H 2 (2-NH 2-5-iPr-3,3 -PBEDDB), G1] 4 nature chemistry

5 supplementary information (a) 4-Iso-propyl-2,6-bis((trimethylsilyl)ethynyl)aniline Under nitrogen gas trimethylsilylacetylene (6.0 ml, 42.0 mmol) was added to a solution of 2,6-dibromo-4-isopropylaniline (5.00 g, 17.0 mmol) in deoxygenated distilled triethylamine (TEA, 40 ml) with tetrakis(triphenylphosphine)palladium(0) (590 mg, 0.50 mmol) and copper(i) iodide (67.0 mg, 0.35 mmol) in a 100 ml Schlenk flask at 0 o C. After stirring for 1 h at room temperature, the reaction system was heated to 60 o C, at which the reaction solution was further stirred for 15 hours. The reaction system was cooled to room temperature and then a saturated aqueous solution of ammonium chloride was added. The aqueous solution was extracted three times with dichloromethane. The combined dichloromethane layer was washed with brine and dried over sodium sulfate. After evaporation of the dichloromethane, the crude residue was purified by column chromatography on silica gel with ethyl acetate/hexane (5%) as eluent to give pure 4-isopropyl-2,6-bis((trimethylsilyl)ethynyl)aniline as a white solid (4.40 g, 80% yield based on 2,6-dibromo-4-isopropylaniline). 1 H NMR (300 MHz, CDCl 3 ): δ 0.26 (s, 18H), 1.16 (d, 6H), 2.72 (m, 1H), 4.69 (s, 2H), 7.14 (s, 2H). (b) 2,6-Diethynyl-4-isopropylaniline A solution of 4-iso-propyl-2,6-bis((trimethylsilyl)ethynyl)aniline (4.40 g, 13.4 mmol) in dichloromethane/methanol (v/v = 1:1, 50 ml) was treated with 4.00 g of K 2 CO 3 at room temperature for 3 h. After removed the solvent water was added and then the system was extracted three times with dichloromethane. The dichloromethane solution was dried over sodium sulfate. After the solvent evaporated, the residue was purified by column chromatography on silica gel with ethyl acetate/hexane (2%) nature chemistry 5

6 supplementary information as eluent to give pure 2,6-diethynyl-4-isopropylaniline as colorless oil (2.30 g, 92% yield). 1 H NMR (300 MHz, CDCl 3 ): δ1.18 (d, 6H), 2.75 (m, 1H), 3.39 (s, 2H), 4.72 (s, 2H), 7.20 (s, 2H). (c) Diethyl 3,3 -(2-amino-5-iso-propyl-1,3-phenylene)bis(ethyne-2,1-diyl)dibenzoate Under nitrogen gas ethyl-3-iodobenzoate (5.2 ml, 31.5 mmol) was added to a solution of 2,6-diethynyl-4-isopropylaniline (2.30 g, 12.6 mmol) in deoxygenated distilled triethylamine (TEA, 40 ml) with tetrakis(triphenylphosphine)palladium(0) (400 mg, 0.35 mmol) and copper(i) iodide (30.0 mg, 0.16 mmol) in a 100 ml Schlenk flask at room temperature. After stirred at reflux temperature for 24 hours, the reaction system was cooled to room temperature, to which a saturated aqueous solution of ammonium chloride and dichloromethane were added. The organic layer was separated and the aqueous layer was further extracted two times with dichloromethane. The combined dichloromethane layer was washed with brine and dried over sodium sulfate. After evaporation of the dichloromethane, the crude residue was purified by column chromatography on silica gel with ethyl acetate/hexane (10%) as eluent to give pure diethyl 3,3 -(2-amino-5-iso-propyl-1,3-phenylene)bis(ethyne-2,1-diyl)dibenzoate as a white solid (4.00 g, 66% yield based on 2,6-diethynyl-4-isopropylaniline). 1 H NMR (300 MHz, CDCl 3 ): δ 1.24 (d, 6H), 1.40 (t, 6H), 2.83 (m, 1H), 4.39 (q, 4H), 4.86(s, 2H), 7.41 (t, 2H), 7.69 (d, 2H), 8.01 (d, 2H), 8.20 (s, 2H). (d) 3,3 -(2-Amino-5-iso-propyl-1,3-phenylene)bis(ethyne-2,1-diyl)dibenzoic acid [H 2 (2-NH 2-5-iPr-3,3 -PBEDDB, G1). Diethyl 3,3 -(2-amino-5-iso-propyl-1,3-phenylene)bis(ethyne-2,1-diyl)dibenzoate (4.00 g, 8.3 mmol) was dissolved in 40 ml of mixed solvent of THF and MeOH (v/v = 1:1), to which 20 ml of 3N NaOH aqueous solution was added. After the mixture stirred at about 50 o C overnight, the organic phase was removed. The aqueous phase was filtrated and acidified with diluted hydrochloric acid to give white precipitate, which was filtered and washed with water to obtain pure 3,3 -(2-amino-5-iso-propyl-1,3-phenylene)bis(ethyne-2,1-diyl)dibenzoic acid (yield: 3.40 g, 95%). 1 H NMR (300 MHz, DMSO-d 6 ): δ 1.18 (d, 6H), 2.78 (m, 1H), 5.72 (s, 2H), 7.28 (s, 2H), 7.56 (t, 2H), 7.87 (d, 2H), 7.89 (d, 2H), 8.20 (s, 2H). FT-IR (neat, cm 1 ): 2960(w), 2871(w), 2546(w), 2197(m), 1686(s), 1600(m), 1578(m), 1488(w), 1439(m), 1418(m), 1362(w), 1310(s), 1251(s), 1232(m), 1166(w), 903(m), 875(s), 810(m), 752(s), 670(s), 660(s) Compound 1 An N,N-dimethylacetamide (DMA) solution (20 ml) of H 2 (5-tBu-1,3-BDC), A1 (445 mg) was mixed 6 nature chemistry

7 supplementary information with a DMA solution (20 ml) of Cu 2 (OAc) 4 H 2 O (400 mg) in a glass vial (50 ml) and stirred for 30 min at room temperature. After that, to this solution 10 ml of MeOH was added and then allowed the vial stand at room temperature. After 20 days homogeneous dark-blue block crystals of [Cu 24 (A) 24 (S) 24 ] xs (1, where S represents solvent molecules throughout this text) were collected and washed with a little MeOH (yield, ~600 mg). FT-IR (neat, cm 1 ): 3392(w), 2966(w), 1626(s), 1584(m), 1438(m), 1374(s), 1272(m), 1120(w), 1113(w), 913(w), 825(w), 777(m), 734(s), 689(w). PXRD of as synthesized 1 is shown in Fig. S7 and TGA in Fig. S29 (Fig. S30 for the sample after gas adsorption measurement). The crystals of 1 slowly lose transparency when solvent molecules evacuated in air for a longer time. This compound is soluble in DEF and NMP, but insoluble in DMA, DMSO, MeOH, THF, acetone, and H 2 O Compound 2 A MeOH (10 ml) solution of H 2 (5-OH-1,3-BDC), B1 (365 mg) was mixed with a MeOH solution (30 ml) of Cu 2 (OAc) 4 H 2 O (400 mg) in a glass vial (50 ml) and stirred for 30 min at room temperature. After that, 10 ml of DMA was added to this solution and then allowed the vial stand at room temperature. After 20 days homogeneous dark-blue block crystals of [Cu 24 (B) 24 (S) 24 ] xs (2) were collected and washed with DMA and a little acetone (yield, ~500 mg). FT-IR (neat, cm 1 ): 3370(w), 2974(w), 1630(s), 1590(s), 1387(s), 1272(w), 1210(w), 1107(w), 1006(w), 897(w), 808(w), 776(s), 735(s), 682(w). PXRD of as synthesized 2 is shown in Fig. S8 and TGA in Fig. S29. The crystals of 2 slowly lose transparency when solvent molecules evacuated in air for a longer time. This compound is soluble in MeOH, but insoluble in H 2 O, EtOH, acetone, DEF, DMA, and DMSO. Crystals of 2 can also be prepared by the reaction of Cu(NO 3 ) 2 2.5H 2 O with H 2 (5-OH-1,3-BDC) in presence of base, 2,6-dimethylpyridine in MeOH/DMA mixed solvent at room temperature, a procedure being similar to that in a MeOH/DMSO solvent system (ref. 30 in the paper) Compound 3 A MeOH (8 ml) solution of NaH 2 (5-SO 3-1,3-BDC), NaC1 (269 mg) was mixed with a MeOH/DMA solution (15 ml, v:v = 1:1) of Cu 2 (OAc) 4 H 2 O (200 mg) in a glass vial (50 ml) and stirred for 10 min at room temperature. After that, 5 ml of DMA was added to this solution and then allowed the vial open and stand at room temperature. After 10 days homogeneous dark-blue block crystals of Na 6 H 18 [Cu 24 (C) 24 (S) 24 ] xs (3) were collected and washed carefully with DMA and a little ethanol (yield, nature chemistry 7

8 supplementary information ~300 mg). FNAA determinations for sodium and copper gave the result of 1.03% of Na and 11.6% of Cu by weight for a crystalline sample of 3, deducing a 1:4 molar ratio of Na:Cu. FT-IR (neat, cm 1 ): 3334(m), 2939(w), 1599(s), 1580(m), 1507(w), 1440(m), 1402(m), 1373(s), 1312(w), 1261(w), 1190(s), 1103(m), 1040(s), 1018(m), 921(w), 878(w), 800(w), 775(m), 732(s), 679(m). PXRD of as synthesized 3 is shown in Fig. S9 and TGA in Fig. S29. The crystals slowly lose transparency when solvent molecules evacuated in air for a longer time. This compound is soluble in MeOH, but insoluble DEF, EtOH, DMA, and DMSO. Similar to that of 2 mentioned above, 3 can also be synthesized by the reaction of Cu(NO 3 ) 2 2.5H 2 O with H 2 (Na5-SO 3-1,3-BDC) in presence of base, 2,6-dimethylpyridine in MeOH/DMA mixed solvent at room temperature Compound 4 As-synthesized crystals of 1 (10 mg) was dissolved in DEF (3.5 ml) to form a blue solution, to which a DEF solution (0.3 ml) of H 2 (3,3 -EDDB), D1 (10 mg) was added and the solution was well-mixed. The resulting solution was allowed to stand at room temperature for 30 days to obtain blue-green block crystals of [Cu 12 (A) 6 (D) 6 (S) 12 ] xs (4) (yield, ~3 mg) associated with a gray-blue suspended substance, which can be easily removed by solvent spilling. The crystals were washed with DEF and a little acetone. FT-IR (neat, cm 1 ): 3414(w), 2974(w), 2875(w), 1657(s), 1622(s), 1592(s), 1425(m), 1393(s), 1306(w), 1259(m), 1216(m), 1109(m), 1080(w), 943(w), 818(m), 773(s), 734(s), 681(w). PXRD of as synthesized 4 is shown in Fig. S10 and TGA in Fig. S29. The similar reactions with only different amounts of H 2 (3,3 -EDDB) from 8 mg to 20 mg were performed in order to evaluate the influence of the amount of H 2 (3,3 -EDDB) on the formation of 4. PXRD of resulting crystals showed that the only compound 4 formed in these systems. This compound is insoluble in MeOH, acetone, H 2 O, DEF, DMA, and DMSO. The crystals slowly lose transparency when solvent molecules evacuated in air for a longer time Compound 5 As-synthesized crystals of 1 (20 mg) was dissolved in DEF (5 ml) to form a blue solution, to which a DEF solution (0.3 ml) of H 2 (2,7-NDC), E1 (15 mg) was added and the solution was well-mixed. The solution was allowed to stand at room temperature for 20 days to obtain blue block crystals of [Cu 24 (A) 12 (E) 12 (S) 24 ] xs (5) (yield, ~13 mg), which were washed with DEF and a little acetone. FT-IR (neat, cm 1 ): 3373(w), 2967(w), 1626(s), 1567(s), 1432(m), 1394(s), 1268(w), 1238(w), 1118(w), 934(w), 8 nature chemistry

9 supplementary information 775(m), 734(m), 691(w), 687(w), 654(m). PXRD of as synthesized 5 is shown in Fig. S11 and TGA in Fig. S29. The similar reactions with only different amounts of H 2 (2,7-NDC) from 12 mg to 35 mg were performed in order to evaluate the influence of the amount of H 2 (2,7-NDC) on the formation of 5. PXRD of resulting crystals showed that the only compound 5 formed in these systems. This compound is insoluble in MeOH, acetone, H 2 O, DEF, DMA, and DMSO. The crystals slowly lose transparency when solvent molecules evacuated in air for a longer time Compound 6 As-synthesized crystals of 2 (30 mg) was dissolved in 3 ml of MeOH to form a blue solution, to which a MeOH solution (2 ml) of H 2 (1,3-BDC), F1 (20 mg) was added and the solution was well-mixed. The solution was allowed to stand at room temperature for 6 days to obtain blue block crystals of [Cu 24 (B) 8 (F) 16 (S) 24 ] xs (6) (yield, ~15 mg), which were washed with MeOH. FT-IR (neat, cm 1 ): 3326(w), 2942(w), 2833(w), 1630(s), 1580(m), 1450(w), 1387(s), 1277(w), 1150(w), 1079(w), 1015(m), 942(w), 832(w), 778(m), 729(s), 663(m). PXRD of as synthesized 6 is shown in Fig. S12 and TGA in Fig. S29. This compound is insoluble in MeOH, acetone, and DEF. The crystals slowly lose transparency when solvent molecules evacuated in air for a longer time. In order to confirm the co-existence of both ligands, 5-OH-1,3-BDC 2 and 1,3-BDC 2 and evaluate the approximate ratio of them in compound 6, the ligand mixture from the degradation of 6 were characterized by 1 H NMR spectrum. 40 mg of as-synthesized crystals of 6 were washed firstly with distilled MeOH five times and then stirred in 2 ml of 2N NaOH aqueous solution at room temperature. After six hours, the resulting black solids were separated by centrifugation to obtain a colorless solution. To the solution 1N HCl aqueous solution was added until ph = 3 and white precipitate formed. The water was removed from the system under vacuum to give a white solid, to which DMSO-d 6 was added for the measurement of the 1 H NMR. As shown in Fig. S1, 1 H NMR result indicated that the ratio of H 2 (5-OH-1,3-BDC) and H 2 (1,3-BDC) is about 1:2, although an absolute evaluation is difficult. nature chemistry 9

10 supplementary information OH HO OH HO OH O O O O Figure S1. 1 H NMR spectrum (DMSO-d 6 ) of mixed ligands from the degradation of Compound 7 In a glass vial as-synthesized crystals of 2 or 3 (25 mg) was dissolved in 3 ml of MeOH, to which a DEF (2 ml) solution of H 2 (2-NH 2-5-iPr-3,3 -PBEDDB), G1 (20 mg) was added and the solution was well-mixed. The solution was allowed to stand at room temperature for 15 days to obtain dark-green block crystals of [Cu 4 (G) 4 (S) 4 ] xs (7) (yield, ~12 mg) associated with a gray-green suspended substance, which can be easily removed by solvent spilling. The crystals were washed with DEF/MeOH mixed solvent and a little EtOH. FT-IR (neat, cm 1 ): 3376(w), 2973(m), 2198(w), 1653(w), 1623(m), 1590(w), 1563(m), 1457(m), 1427(m), 1393(s), 1305(w), 1262(w), 1234(w), 1213(w), 1116(w), 1054(m), 1033(m), 1009(m), 884(w), 823(w), 798(m), 763(s), 676(m). PXRD of as synthesized 7 is shown in Fig. S13 and TGA in Fig. S29. The crystals slowly lose transparence when solvent molecules evacuated in air for a longer time. This compound is soluble in DEF, but insoluble in H 2 O, acetone, EtOH, DMA, and DMSO. 7 can also be synthesized by the direct reaction between H 2 (2-NH 2-5-iPr-3,3 -PBEDDB) and Cu 2 (OAc) 4 H 2 O in MeOH/DEF: both reactants dissolved in DEF were mixed and then MeOH was layered upon the resulting solution, after 5 days, green crystals were harvested. 10 nature chemistry

11 supplementary information Compound 8 Similar to the conversion from 2 or 3 to 7 described above, a MeOH solution (3 ml) of as-synthesized 2 or 3 (20 mg) was mixed with a DEF solution (1.0 ml) of H 2 (9H-3,6-CDC), H1 (20 mg) to give a green solution. The solution was allowed to stand at room temperature for 8 days to obtain green block crystals of [Cu 12 (H) 12 (S) 12 ] xs (8) (yield, ~10 mg), which were washed with acetone. FT-IR (neat, cm 1 ): 3302(w), 2975(w), 1611(s), 1572(m), 1453(w), 1384(s), 1302(m), 1247(w), 1124(m), 1023(w), 913(w), 832(w), 779(s), 733(m), 682(m). PXRD of as synthesized 8 is shown in Fig. S14 and TGA in Fig. S29. This compound is insoluble in MeOH, acetone, and H 2 O, but soluble in DEF, DMA, and DMSO 1. Crystals of 8 can also be obtained from 7 by following a similar procedure to that from 2 or 3 in a 1:1 of MeOH/DEF mixed solvent when H 2 (9H-3,6-CDC) being excess Compound 9 As-synthesized crystals of 8 (10 mg) was dissolved in 2 ml of DMA to form a green solution, to which a DMA solution (0.4 ml) of H 2 (1,3-BDC), F1 (15 mg) was added and the solution was well-mixed. And then the solution was allowed to stand at room temperature for 15 days to obtain dark-blue block crystals of [Cu 24 (F) 24 (S) 24 ] xs (9) (yield, ~6 mg), which were washed with DMA and a little MeOH. FT-IR (neat, cm 1 ): 3384(w), 2930(w), 1614(s), 1452(w), 1387(s), 1267(w), 1190(w), 1079(w), 1020(m), 943(w), 832(w), 746(m), 727(s), 662(m). PXRD of as synthesized 9 is shown in Fig. S15 and TGA in Fig. S29. The similar reactions with only different amounts of H 2 (1,3-BDC) from 12 mg to 30 mg were performed in order to evaluate the influence of the amount of H 2 (1,3-BDC) on the formation of 9. PXRD of resulting crystals showed that the only compound 7 formed in these systems. This compound is insoluble in MeOH, acetone, H 2 O, DEF, DMA, and DMSO and crystals slowly lose transparency when solvent molecules evacuated in air for a longer time Compound 10 A MeOH (10 ml) solution of as synthesized 2 or 3 (60 mg) was mixed with an EtOH solution (8 ml) of H(4-NO 2 -BC), I1 (80 mg) in a glass vial (20 ml). After 5 days homogeneous blue plate crystals of [Cu 2 (I) 4 (EtOH) 2 ] (10) were collected and washed with EtOH (yield, ~50 mg). FT-IR (neat, cm 1 ): 3413(w), 2970(m), 1687(w), 1622(m), 1595(s), 1526(m), 1408(s), 1343(s), 1256(w), 1170(w), 1105(w), 1046(m), 1034(m), 1012(m), 874(m), 832(s), 793(m), 722(s), 675(w). PXRD of as synthesized 10 is shown in Fig. nature chemistry 11

12 supplementary information S16 and TGA in Fig. S29. The crystals are stable in air and soluble in DEF, DMA, and DMSO, but insoluble in H 2 O, MeOH, and EtOH. The direct synthesis and crystal structure of 10 have been reported Control Experiments on the One-Pot Reaction for the Synthesis of MOPs with Mixed Ligands Control experiments to synthesize MOPs (4-6) with mixed ligands by a one-pot self-sorting reaction approach at room temperature have been performed using a typical synthetic procedure: a 1:2 mole ratio of Cu 2 (OAc) 4 H 2 O and corresponding mixed ligand acids were firstly dissolved in selected solvent, respectively. The two solutions were mixed and the mixture was allowed to stand at room temperature. The quantities of metal salt and ligands, the variations of the ratio of two bridging ligands, used solvents, and the quantities of the solvent have been listed in Table S1 for 4, S2 for 5, and S3 for 6, respectively. These reactions have been tracked by photography at three states: after mixing, after 6 days, and after 30 days, as shown in Fig. S2 for 4, S3 for 5, and S4 for 6, respectively. The isolated single crystals have been checked by the determination of unit cell parameters and the results were given below. As demonstrated below, from the one-pot reaction, 4, 5, and 6 can be obtained as single crystals, but always associated with an amorphous blue powder in each case, which was not characterized structurally. 12 nature chemistry

13 supplementary information Table S1 The synthesis of 4 by the one-pot reaction from mixed ligands under various conditions. Solutions of the two ligands and metal salt were mixed in a vial and stood at room temperature. No. Cu 2 (OAc) 4 H 2 O A1 D1 Solvent mmol mg mmol mg mmol mg name ml Result after 30 days DEF 1.3 un-assigned solid DEF and un-assigned solid DEF and un-assigned solid DEF and un-assigned solid DEF and un-assigned solid DEF 2.0 un-assigned solid DEF 2.0 un-assigned solid DEF 2.0 un-assigned solid DEF and un-assigned solid DEF 2.0 un-assigned solid DMF 1.5 un-assigned solid DMSO 1.5 un-assigned solid DMA 1.5 un-assigned solid MeOH 1.5 un-assigned solid MeOH/ DEF(1:1) 1.5 un-assigned solid nature chemistry 13

14 supplementary information Figure S2. The photographs in tracking the reactions for the synthesis of 4 on the one-pot reaction. Single crystals from above reaction systems have been identified by X-ray single-crystal diffraction to give relative unit cell parameters as presented below. Reaction number: 4-2 Reaction number: 4-3 Crystal size (mm 3 ): Crystal size (mm 3 ): Unit cell dimensions: Unit cell dimensions: a (Å) = b (Å) = c (Å) = a (Å) = b (Å) = c (Å) = α ( ) = β ( ) = γ ( ) = α ( ) = β ( ) = γ ( ) = Volume (Å 3 ): Volume (Å 3 ): Crystal system: Triclinic P Crystal system: Triclinic P Reaction number: 4-4 Reaction number: 4-5 Crystal size (mm 3 ): Crystal size (mm 3 ): Unit cell dimensions: Unit cell dimensions: a (Å) = b (Å) = c (Å) = a (Å) = b (Å) = c (Å) = α ( ) = β ( ) = γ ( ) = α ( ) = β ( ) = γ ( ) = Volume (Å 3 ): Volume (Å 3 ): Crystal system: Triclinic P Crystal system: Triclinic P Reaction number: 4-9 Crystal size (mm 3 ): Unit cell dimensions: a (Å) = b (Å) = c (Å) = α ( ) = β ( ) = γ ( ) = Volume (Å 3 ): Crystal system: Triclinic P As shown in above tables, the unit cell parameters of the single-crystal samples from reactions No. 4-2, 14 nature chemistry

15 supplementary information 4-3, 4-4, 4-5, and 4-9 are very close to those of 4 isolated from the bridging-ligand-substitution reaction. This result confirmed that MOP 4 can be obtained as single crystals by the one-pot reaction under suitable conditions, although an uncharacterized amorphous powder was the main product. Reaction conditions are not optimized for preparative purpose. Table S2 The synthesis of 5 by the one-pot reaction from mixed ligands under various conditions. Solutions of the two ligands and metal salt were mixed in a vial and stood at room temperature. No. Cu 2 (OAc) 4 H 2 O A1 E1 Solvent mmol mg mmol mg mmol mg name ml DEF 1.3 Result after 30 days un-assigned small crystals and solid DEF 1.3 un-assigned solid DEF 1.3 un-assigned solid DEF 1.3 un-assigned solid DEF 1.3 un-assigned solid DEF 2.0 un-assigned solid DEF un-assigned solid DEF un-assigned solid DEF un-assigned solid DEF 2.0 un-assigned solid DMF 1.5 un-assigned solid DMSO 1.5 un-assigned solid DMA 1.5 un-assigned solid MeOH 1.5 un-assigned solid MeOH/ DEF(1:1) 1.5 un-assigned solid nature chemistry 15

16 supplementary information Figure S3. The photographs in tracking the reactions for the synthesis of 5 on the one-pot reaction. Single crystals from above reaction systems have been identified by X-ray single-crystal diffraction to give relative unit cell parameters as presented below. Reaction number: 5-1 Crystal size (mm 3 ): Unit cell dimensions: a (Å) = b (Å) = c (Å) = α ( ) = 90 β ( ) = 90 γ ( ) = 90 Collected data are not good enough to determine and refine a structure of this new compound due to the very weak diffraction of the small crystal, notwithstanding we can determine a unit cell from this data set. Volume (Å 3 ): Crystal system: Tetragonal I Reaction number: 5-7 Reaction number: 5-8 Crystal size (mm 3 ): Crystal size (mm 3 ): Unit cell dimensions: Unit cell dimensions: a (Å) = b (Å) = c (Å) = a (Å) = b (Å) = c (Å) = α ( ) = 90 β ( ) = 90 γ ( ) = 90 α ( ) = 90 β ( ) = 90 γ ( ) = 90 Volume (Å 3 ): Volume (Å 3 ): Crystal system: Orthorhombic F Crystal system: Orthorhombic F 16 nature chemistry

17 supplementary information Reaction number: 5-9 Crystal size (mm 3 ): Unit cell dimensions: a (Å) = b (Å) = c (Å) = α ( ) = 90 β ( ) = 90 γ ( ) = 90 Volume (Å 3 ): Crystal system: Orthorhombic F As shown in above tables, the unit cell parameters of the single-crystal samples from reactions No. 5-7, 5-8, and 5-9 are very close to those of 5 isolated from the bridging-ligand-substitution reaction. This result confirmed that MOP 5 can be obtained as single crystals by the one-pot reaction under suitable conditions. Reaction conditions are not optimized for preparative purpose. Table S3 The synthesis of 6 by the one-pot reaction from mixed ligands under various conditions. Solutions of the two ligands and metal salt were mixed in a vial and stood at room temperature. No. Cu 2 (OAc) 4 H 2 O B1 F1 Solvent mmol mg mmol mg mmol mg name ml Result after 30 days MeOH 1.5 un-assigned solid MeOH 1.5 un-assigned solid MeOH 1.5 un-assigned solid MeOH 1.5 un-assigned solid MeOH 1.5 un-assigned solid MeOH 1.8 un-assigned solid MeOH un-assigned solid MeOH 1.8 un-assigned solid MeOH 1.8 un-assigned solid MeOH 1.8 u n-assigned solid DMF 1.5 clear solution DMSO 1.5 clear solution DMA 1.5 un-assigned solid DEF 1.5 un-assigned solid MeOH/ DEF(1:1) 1.5 un-assigned solid nature chemistry 17

18 supplementary information Figure S4. The photographs in tracking the reactions for the synthesis of 6 on the one-pot reaction. Single crystals obtained from above reaction systems have been identified by X-ray single-crystal diffraction to give unit cell parameters as presented below. Reaction number: 6-7 Crystal size (mm 3 ): U nit cell dimensions: a (Å) = b (Å) = c (Å) = α ( ) = 90 β ( ) = γ ( ) = 90 Volume (Å 3 ): Crystal system: Monoclinic C As shown in above tables, the unit cell parameters of the single-crystal sample from the reaction No. 6-7 are very close to those of 6 isolated from the bridging-ligand-substitution reaction. This result confirmed that MOP 6 can be obtained as single crystals by the one-pot reaction under suitable conditions. Reaction conditions are not optimized for preparative purpose. 18 nature chemistry

19 supplementary information 4. X-ray Crystallography (Single-crystal) Single-crystal X-ray diffraction data were collected on a Bruker-AXS APEX-II CCD X-ray diffractometer equipped with a low temperature device and a fine-focus sealed-tube X-ray source (graphite monochromated Mo-K α radiation, λ = Å, ω-scans with a 0.5 o step). Suitable single crystals were directly picked up from the mother liquor, attached to a glass loop and transferred to a designed cold stream of liquid nitrogen (110 K) for data collections. Raw data collection and reduction were done using APEX2 software 3. Absorption corrections were applied using the SADABS routine 4. The structures were solved by direct methods and refined by full-matrix least-squares on F 2 with anisotropic displacement using the SHELXTL software package 5. Non-hydrogen atoms were refined with anisotropic displacement parameters during the final cycles. Hydrogen atoms of ligands were calculated in ideal positions with isotropic displacement parameters. There are large solvent accessible pore volumes in the crystals of MOP molecules 1-9 which are occupied by highly disordered solvent molecules. No satisfactory disorder model could be achieved, and therefore the SQUEEZE program implemented in PLATON was used to remove these electron densities 6. Thus, all of electron densities from free solvent molecules have been squeezed out, while for the coordinated solvent molecules, only oxygen atoms were left and refined. The details of structural refinement before and after SQUEEZE procedure can be found in corresponding Tables S4-12 for 1-9, and Table 13 for 10 without using SQUEEZE. In the process of structural refinement of MOPs 1, 4, and 5, it was found that the carbon atoms of tbu groups have enlarged displacement ellipsoids oriented perpendicular to the plane of the benzene rings. That can be attributed to rotational disorder of the tbu groups around the C tbu -C benz bonds. We refined the occupations of the three positions of carbon atoms corresponding to different dihedral angles between the plane of the aromatic rings and tbu groups. In all cases two positions of tbu groups were modeled successfully; they were refined with the help of restraints on the C C bond length [1.533(1) Å] and displacement parameters, as well as rigid bond restraints for anisotropic displacement parameters. The relative occupancies for the disordered components were refined freely, while constraining the total occupancy of all components to unity. The relative occupancies for the different positions of tbu groups in molecules 1, 4, and 5 can be found in the corresponding CIF files. In the process of structural refinement of the MOP 3, it was found that the O atoms of SO 3 groups have enlarged displacement ellipsoids oriented perpendicular to the plane of the benzene rings. That can be nature chemistry 19

20 supplementary information attributed to rotational disorder of the SO 3 groups around the S C bonds. We refined the occupations of the three positions of oxygen atoms corresponding to different dihedral angles between the plane of the aromatic rings and SO 3 groups. In all cases two positions of SO 3 groups were modeled successfully; they were refined with the help of restraints on S O bond length [1.455(1) Å]) and displacement parameters, as well as rigid bond restraints for anisotropic displacement parameters. The relative occupancies for the disordered components were refined freely, while constraining the total occupancy of all components to unity. The relative occupancies for the different positions of SO 3 groups in molecule 3 can be found in the corresponding CIF file. In addition, the Na + ions are highly disordered and their exact positions can not be determined from the structural refinement. Thus, the electron densities from Na + ions were also squeezed out in the structural refinement. Finally, the structural refinements of MOPs 1-9 were not ideal due to the low quality of crystals and resultant weak diffraction properties. Therefore, PLATON/CHEKCIF procedures of the CIFs give a lot of Alerts A and B. All the alerts were fully explained, and the explanation for each specific alert can be found in the concomitant CIF file or by using on-line PLATON/CHEKCIF service ( Majority of these alerts correspond to the poor anisotropic displacement parameters of the atoms, which are really hard to model by using such low quality diffraction data. Therefore, we cannot detail the molecular geometry of these compounds; however, we can use the results of these experiments to present the qualitative structures of these complex molecules. 20 nature chemistry

21 supplementary information Table S4 Crystal data and structural refinement of 1; for atomic coordinates, equivalent isotropic displacement parameters, bond lengths, angles and anisotropic displacement parameters please see the CIF (CCDC code ). After SQUEEZE Before SQUEEZE Empirical formula C 288 H 288 Cu 24 O 120 C 288 H 288 Cu 24 O 120 Formula weight Temperature (K) 110(2) 110(2) Crystal system Tetragonal Tetragonal Space group I4/mmm I4/mmm Unit cell dimensions a (Å) (9) (9) b (Å) (9) (9) c (Å) 41.22(2) 41.22(2) α ( ) β ( ) γ ( ) Volume (Å 3 ) 35377(23) 35377(23) Z 2 2 Calculated density (mg/m 3 ) Absorption coefficient (mm 1 ) F(000) Crystal size (mm 3 ) Reflections collected Independent reflections 8203 [R(int) = ] 8188 [R(int) = ] Completeness to theta = % 97.1% Data/restraints/parameters 8203/134/ /128/252 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , wr 2 = R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = R 1 = , wr 2 = Largest diff. peak and hole (e.å 3 ) and and nature chemistry 21

22 supplementary information Table S5 Crystal data and structural refinement of 2; for atomic coordinates, equivalent isotropic displacement parameters, bond lengths, angles and anisotropic displacement parameters please see the CIF (CCDC code ). After SQUEEZE Before SQUEEZE Empirical formula C 192 H 96 Cu 24 O 144 C 192 H 96 Cu 24 O 144 Formula weight Temperature (K) 110(2) 110(2) Crystal system Tetragonal Tetragonal Space group I4/m I4/m Unit cell dimensions a (Å) (1) (1) b (Å) (1) (1) c (Å) (3) (3) α ( ) β ( ) γ ( ) Volume (Å 3 ) 26183(2) 26183(2) Z 2 2 Calculated density (mg/m 3 ) Absorption coefficient (mm 1 ) F(000) Crystal size (mm 3 ) Reflections collected Independent reflections [R(int) = ] [R(int) = ] Completeness to theta = % 99.7% Data/restraints/parameters 13029/0/ /0/412 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , wr 2 = R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = R 1 = , wr 2 = Largest diff. peak and hole (e.å 3 ) and and nature chemistry

23 supplementary information Table S6 Crystal data and structural refinement of 3; for atomic coordinates, equivalent isotropic displacement parameters, bond lengths, angles and anisotropic displacement parameters please see the CIF (CCDC code ). After SQUEEZE Before SQUEEZE Empirical formula C 192 H 72 Cu 24 O 192 S 24 C 192 H 96 Cu 24 O 144 Formula weight Temperature (K) 110(2) 110(2) Crystal system Tetragonal Tetragonal Space group I4/m I4/m Unit cell dimensions a (Å) (7) (7) b (Å) (7) (7) c (Å) 41.72(2) 41.72(2) α ( ) β ( ) γ ( ) Volume (Å 3 ) 35190(21) 35190(21) Z 2 2 Calculated density (mg/m 3 ) Absorption coefficient (mm 1 ) F(000) Crystal size (mm 3 ) Reflections collected Independent reflections [R(int) = ] [R(int) = ] Completeness to theta = % 99.4% Data/restraints/parameters 17434/61/ /61/448 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , wr 2 = R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = R 1 = , wr 2 = Largest diff. peak and hole (e.å 3 ) and and nature chemistry 23

24 supplementary information Table S7 Crystal data and structural refinement of 4; for atomic coordinates, equivalent isotropic displacement parameters, bond lengths, angles and anisotropic displacement parameters please see the CIF (CCDC code ). After SQUEEZE Before SQUEEZE Empirical formula C 168 H 120 Cu 12 O 60 C 168 H 120 Cu 12 O 60 Formula weight Temperature (K) 110(2) 110(2) Crystal system Triclinic Triclinic Space group P 1 P 1 Unit cell dimensions a (Å) 26.69(2) 26.69(2) b (Å) 26.71(2) 26.71(2) c (Å) 28.01(2) 28.01(2) α ( ) (8) (8) β ( ) (8) (8) γ ( ) (9) (9) Volume (Å 3 ) 17139(19) 17139(19) Z 2 2 Calculated density (mg/m 3 ) Absorption coefficient (mm 1 ) F(000) Crystal size (mm 3 ) Reflections collected Independent reflections [R(int) = ] [R(int) = ] Completeness to theta = % 98.0% Data/restraints/parameters 62274/100/ /100/1687 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , wr 2 = R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = R 1 = , wr 2 = Largest diff. peak and hole (e.å 3 ) and and nature chemistry

25 supplementary information Table S8 Crystal data and structural refinement of 5; for atomic coordinates, equivalent isotropic displacement parameters, bond lengths, angles and anisotropic displacement parameters please see the CIF (CCDC code ). After SQUEEZE Before SQUEEZE Empirical formula C 288 H 216 Cu 24 O 120 C 288 H 216 Cu 24 O 120 Formula weight Temperature (K) 110(2) 110(2) Crystal system Orthorhombic Orthorhombic Space group Fddd Fddd Unit cell dimensions a (Å) (3) (3) b (Å) (6) (6) c (Å) (8) (8) α ( ) β ( ) γ ( ) Volume (Å 3 ) (23) (23) Z 8 8 Calculated density (mg/m 3 ) Absorption coefficient (mm 1 ) F(000) Crystal size (mm 3 ) Reflections collected Independent reflections [R(int) = ] [R(int) = ] Completeness to theta = % 99.5% Data/restraints/parameters 30679/267/ /267/796 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , wr 2 = R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = R 1 = , wr 2 = Largest diff. peak and hole (e.å 3 ) and and nature chemistry 25

26 supplementary information Table S9 Crystal data and structural refinement of 6; for atomic coordinates, equivalent isotropic displacement parameters, bond lengths, angles and anisotropic displacement parameters please see the CIF (CCDC code ). After SQUEEZE Before SQUEEZE Empirical formula C 192 H 98 Cu 24 O 128 C 192 H 98 Cu 24 O 128 Formula weight Temperature (K) 110(2) 110(2) Crystal system Monoclinic Monoclinic Space group C2/c C2/c Unit cell dimensions a (Å) 35.49(3) 35.49(3) b (Å) 32.46(2) 32.46(2) c (Å) 35.61(3) 35.61(3) α ( ) β ( ) 92.42(1) 92.42(1) γ ( ) Volume (Å 3 ) 40986(55) 40986(55) Z 4 4 Calculated density (mg/m 3 ) Absorption coefficient (mm 1 ) F(000) Crystal size (mm 3 ) Reflections collected Independent reflections [R(int) = ] [R(int) = ] Completeness to theta = % 99.3% Data/restraints/parameters 41904/88/ /88/1513 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , wr 2 = R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = R 1 = , wr 2 = Largest diff. peak and hole (e.å 3 ) and and nature chemistry

27 supplementary information Table S10 Crystal data and structural refinement of 7; for atomic coordinates, equivalent isotropic displacement parameters, bond lengths, angles and anisotropic displacement parameters please see the CIF (CCDC code ). After SQUEEZE Before SQUEEZE Empirical formula C 108 H 76 Cu 4 N 4 O 20 C 108 H 76 Cu 4 N 4 O 20 Formula weight Temperature (K) 110(2) 110(2) Crystal system Monoclinic Monoclinic Space group P2 1 /n P2 1 /n Unit cell dimensions a (Å) (1) (1) b (Å) (2) (2) c (Å) (2) (2) α ( ) β ( ) (1) (1) γ ( ) Volume (Å 3 ) 14695(2) 14695(2) Z 4 4 Calculated density (mg/m 3 ) Absorption coefficient (mm 1 ) F(000) Crystal size (mm 3 ) Reflections collected Independent reflections [R(int) = ] [R(int) = ] Completeness to theta = % 99.5% Data/restraints/parameters 30379/44/ /44/727 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , wr 2 = R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = R 1 = , wr 2 = Largest diff. peak and hole (e.å 3 ) and and nature chemistry 27

28 supplementary information Table S11 Crystal data and structural refinement of 8; for atomic coordinates, equivalent isotropic displacement parameters, bond lengths, angles and anisotropic displacement parameters please see the CIF (CCDC code ). After SQUEEZE Before SQUEEZE Empirical formula C 168 H 84 Cu 12 N 12 O 60 C 168 H 84 Cu 12 N 12 O 60 Formula weight Temperature (K) 110(2) 110(2) Crystal system Triclinic Triclinic Space group P 1 P 1 Unit cell dimensions a (Å) (6) (6) b (Å) (7) (7) c (Å) (7) (7) α ( ) (4) (4) β ( ) (4) (4) γ ( ) (4) (4) Volume (Å 3 ) 7623(4) 7623(4) Z 1 1 Calculated density (mg/m 3 ) Absorption coefficient (mm 1 ) F(000) Crystal size (mm 3 ) Reflections collected Independent reflections [R(int) = ] [R(int) = ] Completeness to theta = % 98.5% Data/restraints/parameters 26907/0/ /0/1099 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , wr 2 = R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = R 1 = , wr 2 = Largest diff. peak and hole (e.å 3 ) and and nature chemistry

29 supplementary information Table S12 Crystal data and structural refinement of 9; for atomic coordinates, equivalent isotropic displacement parameters, bond lengths, angles and anisotropic displacement parameters please see the CIF (CCDC code ). After SQUEEZE Before SQUEEZE Empirical formula C 192 H 96 Cu 24 O 120 C 192 H 96 Cu 24 O 120 Formula weight Temperature (K) 110(2) 110(2) Crystal system Triclinic Triclinic Space group P 1 P 1 Unit cell dimensions a (Å) (2) (2) b (Å) (2) (2) c (Å) (3) (3) α ( ) (1) (1) β ( ) (1) (1) γ ( ) (1) (1) Volume (Å 3 ) 11774(2) 11774(2) Z 1 1 Calculated density (mg/m 3 ) Absorption coefficient (mm 1 ) F(000) Crystal size (mm 3 ) Reflections collected Independent reflections [R(int) = ] [R(int) = ] Completeness to theta = % 99.3% Data/restraints/parameters 44979/0/ /0/1369 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , wr 2 = R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = R 1 = , wr 2 = Largest diff. peak and hole (e.å 3 ) and and nature chemistry 29

30 supplementary information Table S13 Crystal data and structural refinement of 10; for atomic coordinates, equivalent isotropic displacement parameters, bond lengths, angles and anisotropic displacement parameters please see the CIF (CCDC code ). Empirical formula C 32 H 26 Cu 2 N 4 O 18 Formula weight Temperature (K) 110(2) Crystal system Triclinic Space group P 1 Unit cell dimensions a (Å) 6.590(1) b (Å) (2) c (Å) (2) α ( ) (2) β ( ) (2) γ ( ) (2) Volume (Å 3 ) 865.4(3) Z 1 Calculated density (mg/m 3 ) Absorption coefficient (mm 1 ) F(000) 448 Crystal size (mm 3 ) Reflections collected 7851 Independent reflections 3353 [R(int) = ] Completeness to theta = % Data/restraints/parameters 3353/0/248 Goodness-of-fit on F Final R indices [I > 2σ(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole (e.å 3 ) and nature chemistry