SUPPLEMENTARY INFORMATION

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1 SUPPLEMENTARY INFORMATION Selective Sorption of Oxygen and Nitric Oxide by an Electron-Donating Flexible Porous Coordination Polymer Satoru Shimomura, 1 Masakazu Higuchi, 2 Ryotaro Matsuda, 3,4 Ko Yoneda, 1 Yuh Hijikata, 1 Yoshiki Kubota, 2,5 Yoshimi Mita, 6 Jungeun Kim, 7 Masaki Takata, 2,7 Susumu Kitagawa, 1,2,3,4. 1 Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Kyoto , Japan 2 RIKEN, SPring-8 center, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo , Japan 3 ERATO Kitagawa Integrated Pores Project (Japan), Kyoto Research Park Bldg #3, Shimogyo-ku, Kyoto , Japan 4 Institute for Integrated Cell-Material Sciences, Kyoto University 69 Konoe-cho, Yoshida, Sakyo-ku, Kyoto , Japan 5 Department of Physical Science, Graduate School of Science, Osaka Prefecture University, Osaka , Japan 6 Division of Materials Physics, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka , Japan, 7 Japan Synchrotron Radiation Research Institute, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo , Japan. kitagawa@sbchem.kyoto-u.ac.jp Additional Experimental Section Synthesis of [Zn(TCNQ-TCNQ)bpy] 1.5benzene (1 benzene). Slow addition of a solution of LiTCNQ (2 mmol, 422 mg) and bpy (1 mmol, 156 mg) in MeOH/benzene mixture (1:1, 100 ml) to a solution of Zn(NO 3 ) 2 6H 2 O (1 mmol, 297 mg) in MeOH/benzene mixture (1:1, 100 ml) at 293 K under N 2 atmosphere. The green powder obtained was collected by filtration, washed with MeOH/benzene mixture (1:20), and dried under reduced pressure. (yield 93%) Elemental analysis calcd. for C 43 H 25 N 10 Zn: C, 69.17; H, 3.37; N, 18.75, Found: C, 68.48; H, 3.58; N, The compound accommodating other aromatic guests are synthesized by a method similar to 1 benzene with using other aromatic molecule as a solvent instead of benzene. Crystal Structure Determination nature chemistry 1

2 supplementary information Single crystal X-ray diffraction data collection was carried out on a Rigaku mercury diffractometer with a graphite monochromated MoK radiation ( = Å) and a CCD detector. The crystal structure was solved by a direct method (SHELX97) and refined by full-matrix least-squares refinement using the CRYSTALS computer program. The positions of non-hydrogen atoms were refined with anisotropic displacement factors, except for the guest molecules. The hydrogen atoms were positioned geometrically and refined using a riding model. The void space of all compounds along the c axis is occupied by the disordered guest molecules. The case of 1 1,2,4,5-tetrafluorobenzene, Due to the disorder of the guest molecules, U(eq) of the some atoms of guest molecules are underestimated. The other alerts derive from the disordered guest molecules which could not be completely decided the positions. CCDC contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via Theoretical approach The total stabilization energy depending on the distance between one TCNQ dimer and single gas molecules have been calculated at MP2/6-311+G* level. However NO shows a higher affinity for TCNQ dimer than the other gas molecules, we cannot get the results suggesting the primacy of O 2 over the other molecules and supporting the experimental results. These results imply the selective sorption of this compound should not be based on the interaction between single TCNQ dimer and single gas molecules but the other mechanism, such as the interaction between TCNQ dimers and aggregated gas molecules. Relatively high gate opening pressure of O 2 sorption isotherm is consistent with this assumption. About the sorption measurements and the isotherms of 1 The measurement method is as below: Measurer decides recorded points with an introduction pressure (P i ) of an adsorptive. P i of an adsorptive is introduced into the cell and then it will achieve an equilibrium pressure (P e ). When the pressure change is less than 0.2 % of P 1 during 1200 sec, P e is determined. Then, the adsorption amount (A) are calculated and P e and A are recorded. In this one cycle, there is no additional vapor-dosing of an adsorptive into the cell. The compound we have is a sort of soft crystal, which responds to guest molecules and change its structure on the sorption. Therefore, this is not the case that robust framework adsorbs guests without any structural changes. The guest incorporation induce structural changes, therefore, the guest-sorption comprises of kinetic phenomena. This is well-discussed in published papers. 1,2 In the transformable porous system, it is difficult to obtain the isotherm in the finite duration of experiments because of the complex kinetic process in which guest accommodation and 2 nature chemistry

3 supplementary information structural transformation proceed simultaneously. We reported that the gated sorption phenomena strongly depend on the kinetics of transformation. In the transformable porous system, it is difficult to obtain the isotherm in the finite duration of experiments because of the complex kinetic process in which guest accommodation and structural transformation proceed simultaneously. We reported that the gated sorption phenomena strongly depend on the kinetics of transformation. 3 Figure S3 shows the O 2 adsorption curve and time dependent pressure change of this compound. The first pronounced decrease of pressure has been observed between point 4 and 5. Due to the kinetic effects of gate opening process with structural transformation, the rate of pressure decrease between point 4 and 5 is slower than the rate after point 5. In the results, we get the adsorption curve with the backward movement like Figure S2. nature chemistry 3

4 supplementary information Table S1. Crystal data and Structure Solution and Refinement of 1 anisole. Empirical Formula Formula Weight Crystal System Lattice Parameters C 41 H 16 N 10 OZn orthorhombic a = (4) Å b = (5) Å c = (5) Å V = (13) Å 3 Space Group Pccm (#49) Z value 2 Dcalc g/cm 3 F (MoK ) cm -1 Radiation MoK ( = Å) graphite monochromated 2 max No. of Reflections Measured Total: Unique: 2548 (Rint = 0.022) Completeness 99.8% Refinement 2 max cutoff Anomalous Dispersion No. Observations (I>2.50 (I)) 2130 No. Variables 156 Reflection/Parameter Ratio Residuals: R1 (I>2.00 (I)) Residuals: wr2 (All reflections) Goodness of Fit Indicator Max Shift/Error in Final Cycle Maximum peak in Final Diff. Map 1.67 e /Å 3 Full-matrix least-squares on F All non-hydrogen atoms Minimum peak in Final Diff. Map 0.75 e /Å 3 4 nature chemistry

5 supplementary information Table S2. Crystal data and Structure Solution and Refinement of 1 benzonitrile. Empirical Formula Formula Weight Crystal System Lattice Parameters C 41 H 20 N 11 Zn orthorhombic a = (13) Å b = (14) Å c = (14) Å V = (4) Å 3 Space Group Pccm (#49) Z value 2 Dcalc g/cm 3 F (MoK ) cm -1 Radiation MoK ( = Å) graphite monochromated 2 max No. of Reflections Measured Total: Unique: 2527 (Rint = 0.020) Completeness 99.8% Refinement 2 max cutoff Anomalous Dispersion No. Observations (I>2.00 (I)) 2223 No. Variables 148 Reflection/Parameter Ratio Residuals: R1 (I>2.00 (I)) Residuals: wr2 (I>2.00 (I)) Goodness of Fit Indicator Max Shift/Error in Final Cycle Maximum peak in Final Diff. Map 1.66 e /Å 3 Full-matrix least-squares on F All non-hydrogen atoms Minimum peak in Final Diff. Map 0.37 e /Å 3 nature chemistry 5

6 supplementary information Table S3. Crystal data and Structure Solution and Refinement of 1 p-xylene. Empirical Formula Formula Weight Crystal System Lattice Parameters C 42 H 26 N 10 Zn orthorhombic a = (17) Å b = (19) Å c = (2) Å V = (6) Å 3 Space Group Pccm (#49) Z value 2 Dcalc g/cm 3 F (MoK ) cm -1 Radiation MoK ( = Å) graphite monochromated 2 max No. of Reflections Measured Total: Unique: 2561 (Rint = 0.052) Completeness 99.8% Refinement 2 max cutoff Anomalous Dispersion No. Observations (I>3.00 (I)) 1587 No. Variables 146 Reflection/Parameter Ratio Residuals: R1 (I>3.00 (I)) Residuals: Rw (I>3.00 (I)) Goodness of Fit Indicator Max Shift/Error in Final Cycle Maximum peak in Final Diff. Map 2.04 e /Å 3 Full-matrix least-squares on F All non-hydrogen atoms Minimum peak in Final Diff. Map 0.40 e /Å 3 6 nature chemistry

7 supplementary information Table S4. Crystal data and Structure Solution and Refinement of 1 1,2,4,5-Tetrafluorobenzene. Empirical Formula Formula Weight Crystal System Lattice Parameters C 46 H 16 N 10 F 8 Zn orthorhombic a = (6) Å b = (3) Å c = (4) Å V = 4211(2) Å 3 Space Group Pcca (#54) Z value 4 Dcalc g/cm 3 F (MoK ) cm -1 Radiation MoK ( = Å) graphite monochromated 2 max No. of Reflections Measured Total: Unique: 4648 (Rint = 0.019) Completeness 99.8% Refinement 2 max cutoff Anomalous Dispersion No. Observations (I>3.00 (I)) 3526 No. Variables 327 Reflection/Parameter Ratio Residuals: R1 (I>3.00 (I)) Residuals: Rw (I>3.00 (I)) Goodness of Fit Indicator Max Shift/Error in Final Cycle Maximum peak in Final Diff. Map 1.92 e /Å 3 Full-matrix least-squares on F All non-hydrogen atoms Minimum peak in Final Diff. Map 0.79 e /Å 3 nature chemistry 7

8 supplementary information Table S5. The dimensions of the gas molecules NO CO2 C2H2 Ar O2 N2 CO Dimension X (Å) Y (Å) Z (Å) Webster, C. E., Drago, R. S., and Zerner, M. C. Molecular Dimensions for adsorptive. J. Am. Chem. Soc. 120, (1998). 8 nature chemistry

9 supplementary information Figures Figure S1. Results of Le Bail analysis for each state of 1. Red plus marks and blue solid lines show the observed and calculated X-ray powder diffraction patterns for (a) NO adsorbed state, (b) O 2 adsorbed state, and (c) no guest state. The open triangle marks indicate the position of Bragg peaks, and the green solid lines at the bottom correspond to the difference between observed and calculated intensities. nature chemistry 9

10 supplementary information Figure S3. (a)(b) The O 2 adsorption curve and the detail around the gate opening process. (c)(d) The time dependent pressure change in this measurement and the detail around the gate opening process. The labeled numbers of each point in (b) are directly corresponded to in (d). 10 nature chemistry

11 supplementary information References 1. Coudert, F. X., Jeffroy, M., Fuchs, A. H., Boutin, A., and Mellot-Draznieks, C. Thermodynamics of Guest-induced Structural Transitions in Hybrid Organic-Inorganic Frameworks. J. Am. Chem. Soc. 130, (2008). 2. Watanabe, S., Sugiyama, H., Adachi, H., Tanaka, H., and Miyahara, M. T. Free energy analysis for adsorption-induced lattice transition of flexible coordination framework. J. Chem. Phys. 130, - (2009). 3. Tanaka, D. et al. Kinetic gate-opening process in a flexible porous coordination polymer. Angew. Chem. Int. Ed. 47, (2008). nature chemistry 11