A novel series of isoreticular metal organic frameworks: realizing metastable structures by liquid phase epitaxy

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1 A novel series of isoreticular metal organic frameworks: realizing metastable structures by liquid phase epitaxy Supplementary Information Jinxuan Liu (1), Binit Lukose(2), Osama Shekhah (1,3), Hasan Kemal Arslan (1), Peter Weidler (1), Hartmut Gliemann (1), Stefan Bräse (4, 5), Sylvain Grosjean (4, 5), Adelheid Godt (6), Xinliang Feng (7), Klaus Müllen (7), Ioan Bogdan Magdau (1,2), Thomas Heine(2,*), Christof Wöll (1,*) (1) Institute of Functional Interfaces, Karlsruhe Institute of Technology, Eggenstein Leopoldshafen, Germany. E Mail: christof.woell@kit.edu (2) School of Engineering and Science, Jacobs University Bremen, Bremen, Germany, E Mail: t.heine@jacobs university.de (3) Advanced Membranes & Porous Materials Center, King Abdullah University of Science and Technology, Thuwal, , Kingdom of Saudi Arabia. (4) Institute of Organic Chemistry, Karlsruhe Institute of Technology, Karlsruhe, Germany. (5) Soft Matter Synthesis Lab, Institute for Biological Interfaces, Karlsruhe Institute of Technology, Eggenstein Leopoldshafen, Germany. (6) Department of Chemistry, Bielefeld University, Bielefeld, Germany. (7) Max Plank Institut für Polymerforschung, Ackermannweg 10, 55128, Mainz, Germany. Synthesis of organic linkers (1) para terphenyldicarboxylic acid (TPDC) Following the synthesis described by Campbell et al. 1 to a solution of para terphenyl (purchased from ABCR, g, 6.51 mmol) and oxalyl chloride (3.350 ml, mmol) in carbon disulfide (30 ml) at 0 C (ice bath) was added aluminium chloride (1.475 g, mmol). After 1h of stirring, additional aluminium chloride (0.870 g, 6.51 mmol) was added, the ice bath was removed and the reaction mixture was stirred at room temperature for 24h. The mixture was poured into crushed ice and stirred until the dark brown mixture turned to yellow. Carbon disulfide was removed under reduced pressure, and the resulting aqueous suspension was filtered. The solid was washed with diluted hydrochloric acid, then with diethyl ether, and dried under vacuum overnight with an oil bath at 50 C. A pale yellow solid (2.03 g, 98%) was obtained. 1 H NMR (CDCl 3, 300MHz, 298K): δ (ppm) 8.23 (d, J = 8.2Hz, 4H), 7.79 (d, J = 8.2Hz, 4H), 7.78 (m, 4H); 13 C NMR (CDCl 3, 75MHz, 298K): δ (ppm) 168.2, 147.2, 139.7, 132.4, 132.3, 128.2, MS (EI, 70 ev): m/z 318. Melting point: > 400 C. (2) para quaterphenyldicarboxylic acid (QPDC) Following the synthesis described previously 1 to a solution of para quaterphenyl (purchased from ABCR, g, 3.26 mmol) and oxalyl chloride (1.680 ml, mmol) in carbon disulfide (20 ml) at 0 C (ice bath) was added aluminium chloride (0.740 g, 5.55 mmol). After 1h stirring, additional aluminium chloride (0.435 g, 3.26 mmol) was added, the ice bath was removed and the reaction mixture was stirred at room temperature for 24h. The mixture was poured into crushed ice and stirred until the dark brown mixture turned to yellow. Carbon disulfide was removed under reduced

2 pressure, and the resulting aqueous suspension was filtered. The solid was washed with hydrochloric acid, then with diethyl ether, and dried under vacuum overnight with an oil bath at 50 C. A yellow solid (1.19 g, 92%) was obtained. 1 H NMR (CDCl 3, 300MHz, 298K): δ (ppm) 8.22 (d, J = 8.7Hz, 4H), 7.80 (d, J = 8.7Hz, 4H), 7.78 (m, 8H); 13 C NMR (CDCl 3, 75MHz, 298K): δ (ppm) 159.8, 132.3, 128.1, 127.9, HRMS (EI, 70 ev): m/z , cacld.: IR (ATR platinium Diamond) 3050, 2926, 1677, 1597, 1482, 1399, Melting point: > 400 C. (3) P(EP) 2 DC The synthesis of the P(EP) 2 DC linker has been described in Ref. 2 (4) para pentaphenyl dicarboxylic acid (PPDC) COOMe COOH OH Br Br + MeOOC B OH i ii COOMe COOH Scheme 1. Synthesis of para pentaphenyl dicarboxylic acid. i) Pd(PPh 3 ) 4, Na 2 CO 3, toluene/dioxane/h 2 O, 85 o C; ii) MeOH, 6M NaOH; HCl. Para pentaphenyl dicarboxylic acid was synthesized via Suzuki coupling of 4,4 dibromo p terphenyl and 4 methoxycarbonylphenylboronic acid (Scheme 1). 4,4 Dibromo p terphenyl (776 mg, 2.00 mmol), 4 methoxycarbonylphenylboronic acid (1.08 g, 6.0 mmol) and Na 3 CO 3 (1.70 g, 16.0 mmol) were added to a degassed mixture of toluene/1,4 dioxane (50 ml, 2:2:1) under Ar. [Pd(PPh 3 ) 4 ] (116 mg, 0.10 mmol) was added to the mixture and the reaction mixture was heated to 85 C for 24 hours under Ar. The reaction mixture was cooled to room temperature. The precipitate was collected by filtration, washed with water, methanol and used for next reaction without further purification. The final product PPDC was obtained by hydrolysis of the crude product under reflux in methanol (100 ml) overnight with 6M aqueous NaOH (20 ml) followed by acidification with HCl (conc.). After removal of methanol, the final product was collected by filtration as a grey solid (0.78 g, 83%). 1 H NMR (d 6 DMSO, 250MHz, 298K): δ (ppm) 8.05 (d, J = 7.5Hz, 4H), (m, 12H), 7.50 (d, J = 7.5Hz, 4H); 13 C NMR cannot be clearly resolved due to poor solubility. MALDI TOF MS (TCNQ as matrix): m/z , cacld.: Elemental analysis: Calculated: C 81.69, H 4.71; Found: C 81.63, H 4.79.

3 Figure S1: MOF 2 in P4 (as reported), P2 and C2 symmetry.

4 Figure S2: In plane XRD data of Cu BDC, Cu 2,6 NDC, Cu BPDC, Cu TPDC, Cu QPDC and Cu P(EP) 2 DC. All the SURMOF 2 are grown on COOH terminated SAM surface using the LPE method. The position of (010) plane represents the layer distance.

5 6 Cu-QPDC(SURMOF) 6 Cu-QPDC (SURMOF) 4 P4 4 P4 Intensity 2 C2 P2 Intensity 2 C2 P2 Cu(QPDC)(DMF) Cu(QPDC)(DMF) Cu(QPDC)(EtOH) Cu(QPDC)(EtOH) ,0 2,5 3,0 3,5 4,0 4,5 5,0 5,5 6,0 2 / o 2 / o Fig.S3 Powder XRD data of Cu(QPDC)(EtOH) and Cu(QPDC)(DMF) synthesized using the solvothermal method described in Eur. J. Inorg. Chem. 2009, For the purpose of comparison simulated XRD data of Cu QPDC with P2, C2 and P4 structures are shown as well. Table 1: Stacking energy and geometries of P4 SURMOF 2 derivatives Symmetry a= c b Stacking Energy* Cu 2 (bdc) 2 C Cu 2 (bdc) 2 P Cu 2 (bdc) 2 P Cu 2 (ndc) 2 P Cu 2 (bpdc) 2 P Cu 2 (tpdc) 2 P Cu 2 (qpdc) 2 P Cu 2 (P(EP) 2 DC) 2 P Cu 2 (ppdc) 2 P * Stacking energies (DFTB level, in ev) of SURMOFs. The energies were calculated within periodic boundary conditions and are given per formula unit. References 1 Campbell, T.W., Dicarboxylation of Terphenyl. J Am Chem Soc 82, (1960). 2 Schaate, A. et al., Porous Interpenetrated Zirconium Organic Frameworks (PIZOFs): A Chemically Versatile Family of Metal Organic Frameworks. Chemistry a European Journal 17, (2011).

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