Supporting Information Crystal surface mediated structure transformation of kinetic framework composed of multi-interactive ligand TPHAP and Co(II) Yumi Yakiyama, Akira Ueda, Yasushi Morita,* Masaki Kawano* Contents of Supplementary Information: 1. Methods Synthesis of K + TPHAP Syntheses of TPHAP-Co Kin, TPHAP-Co Therm -1 and TPHAP-Co- Therm -2 X-ray crystallographic data S2 S2 S3 2. Figures S1 S11 Fig. S1 ORTEP view of K + TPHAP CH 3 OH S5 Fig. S2 The N HO type hydrogen bonding interactions in a pore of TPHAP-Co Kin S5 Fig. S3 The N HO type hydrogen bonding interactions in a pore of TPHAP-Co Therm -1 S6 Fig. S4 AFM images of the surface of single crystal Co-TPHAP Kin S6 Fig. S5 The bond lengths of HAP skeletons in TPHAP-Co Kin crystal S7 Fig. S6 The bond lengths of HAP skeletons in two thermodynamically more stable crystals S7 Fig. S7 IR spectrum of K + TPHAP S8 Fig. S8 The face index of TPHAP-Co Kin crystal and the model picture S8 Fig. S9 The crystal structure of TPHAP-Co Therm -2 S9 Fig. S10 Temperature-dependent X-ray diffraction pattern change of TPHAP-Co Therm -1 S9 Fig. S11 The simulated void spaces of TPHAP-Co systems S10 Fig. S12 The CCD 2D-images of TPHAP-Co Kin crystals and the capillary pictures before and after in situ study S11 3. Reference S12 S1
Methods All chemicals and reagents were used as received. All reactions were performed at ambient temperature in air. UV/vis spectra were recorded on a Shimadzu UV/Vis-NIR scanning spectrophotometer UV-3600 PC using methanol solution (1.0 x 10 5 M). IR spectra were recorded on a Varian 670-IR FT-IR spectrometer in KBr pellets. The diffraction data for K + TPHAP were collected on a Bruker APEX II QUAZAR instrument in house. The diffraction data for TPHAP-Co Kin, TPHAP-Co Therm -1, and TPHAP-Co Therm -2 were collected on a RIGAKU/MSC Mercury CCD X-ray diffractometer with a synchrotron radiation ( = 0.6889 Å) at PF-AR (NW2A beamline) of the High Energy Accelerator Research Organization (KEK). The structures were solved by direct methods (SHELXS-97) and refined by full-matrix least squares calculations on F 2 (SHELXL-97) using the SHELX-TL program package. Elemental analyses were performed at Pohang University of Science and Technology. AFM images collection of TPHAP-Co Kin crystals AFM images of TPHAP-Co Kin crystals were measured on a VEECO Dimension 3100+Nanoscope V (Version 7.0) at National Center for Nanomaterials Technology (NCNT, Korea). After shaking the crystallization tube, we immediately picked up the single crystals and casted on a Si wafer after washing with EtOH twice. The images in 5 min or 10 min after shaking were also measured in the same way. Powder X-ray diffraction of TPHAP-Co crystals In situ powder X-ray diffraction of TPHAP-Co Kin crystals: Dozens of single crystals of TPHAP-Co Kin were loaded into a 0.7 mm capillary with a mother solution of the crystallization. In situ powder data were collected at 25 C on a Bruker APEX II QUAZAR instrument in house: the X-ray beam size, 100 m; scan, 360 rotation; exposure time, 180 sec. The 2D diffraction images were integrated with the FIT2D program to generate 1D powder diffraction data S1 If a mother solution of the crystallization for TPHAP-Co Kin was not provided enough, crystal transformation was not completed, leading to mixture of TPHAP-Co Kin and TPHAP-Co Therm -1. During diffraction measurement, a capillary was regularly shuffled by moving -axis to provide the mother solution to crystals and promote structure transformation smoothly. Temperature-dependent X-ray diffraction pattern change of TPHAP-Co Therm -1: Dozens of single crystals of TPHAP-Co Therm -1 were loaded into a 0.7 mm capillary with a mother solution of the crystallization. The crystals were collected and measured at 25 C firstly, then heated at 40 C for 12 h. The image data were collected at 25 C on a Bruker APEX II QUAZAR instrument in house: the X-ray beam size, 100 m; scan, 360 rotation; exposure time, 180 sec. The 2D diffraction images were integrated with the FIT2D program to generate 1D powder diffraction data. Synthesis of potassium 2,5,8-tri-(4 -pyridyl)-1,3,4,6,7,9-hexaazaphenalenate, K + TPHAP : 4-pyridylamidine hydrochloride (9.10 g, 57.7 mmol) and potassium tricyanomethanide (1.50 g, 11.6 mmol) were placed in a Teflon-lined stainless autoclave and heated at 200 ºC for 16 h. At this stage, a NMR yield of the product is about 62%. A 2M HCl aqueous solution was added to the reaction S2
mixture and washed with ethyl acetate. After removing ethyl acetate, the aqueous layer was neutralized with a 5M KOH aqueous solution. The resultant solid was collected and purified with MeOH/ethyl acetate to give the salt as brownish yellow powder (2.23 g, 43%). m.p. > 300 C; 1 H NMR: = 8.39 (d, 6H, J = 20 Hz), 8.77 (d, 6H, J = 20 Hz); 13 C NMR: = 10.76, 122.27, 146.31, 150.11, 166.00, 166.73; UV/Vis (methanol): max = 326 nm; elemental analysis calcd (%) for C 23 H 17.2 N 9 O 1.6 K (=C 22 H 12 N 9 K(CH 3 OH)(H 2 O) 0.6 ): C, 57.04; H, 3.58; N, 26.03. Found: C, 56.66; H, 3.40; N, 26.43. Synthesis of Co II network of [Co(TPHAP ) 2 (CH 3 OH) 2 (H 2 O)] 3C 6 H 5 NO 2 HNO 3 5H 2 O (TPHAP-Co Kin ): The single crystals were grown from a double-layered solution consisting of a methanol solution of Co(NO 3 ) 2 6H 2 O (131.5 mm) as the top layer, and a nitrobenzene/methanol solution (volume ratio: nitrobenzene:methanol = 7:1) of K + TPHAP (12.8 mm) as the bottom layer at 14 C. After 1 day, pale red crystals were grown. As keeping more than 2 days or giving a shock can cause the transformation to TPHAP-Co Therm -1, all crystals are collected at this moment. The isolated yield was 21% yield (based on the amount of K + TPHAP ). This low yield comes from the high reactivity of TPHAP-Co Kin. Elemental analysis calcd (%) for C 64 H 60 N 22 O 17 Co(=(C 22 H 12 N 9 ) 2 (Co)(CH 3 OH) 2 (C 6 H 5 NO 2 ) 3 (HNO 3 )(H 2 O) 6 ): C, 52.35; H, 4.12; N, 20.99. Found: C, 52.18; H, 3.83; N, 20.64. Synthesis of single crystal of [Co(NO 3 )(TPHAP )(CH 3 OH) 2 ] CH 3 OH C 6 H 5 NO 2 2HNO 3 H 2 O (TPHAP-Co Therm -1): The single crystals of (TPHAP-Co Therm -1) were prepared by the structural transformation of a kinetic crystal of [Co(TPHAP ) 2 (CH 3 OH) 2 (H 2 O)] 3C 6 H 5 NO 2 HNO 3 5H 2 O, just leaving the crystallization tube for more than two days. The isolated yield is 31% (calculated based on the amount of K + TPHAP ). Elemental analysis calcd (%) for C 31 H 21 N 13 O 15 Co (= (C 22 H 12 N 9 )(Co)(CH 3 OH) 3 (C 6 H 5 NO 2 )(NO 3 )(HNO 3 ) 2 (H 2 O)): C, 42.09; H, 3.53; N, 20.58. Found: C, 42.22; H, 3.64; N, 20.79. Synthesis of single crystal of [Co(NO 3 )(TPHAP )(CH 3 OH)] CH 3 OH 2.5(C 6 H 5 NO 2 ) H 2 O (TPHAP-Co Therm -2): The single crystals were grown from a double-layered solution consisting of a methanol solution of Co(NO 3 ) 2 6H 2 O (131.5 mm) as the top layer, and a nitrobenzene/methanol solution (volume ratio: nitrobenzene:methanol = 7:1) of K + TPHAP (12.8 mm) as the bottom layer at 25 C. After 1 day, dark red crystals were grown and isolated in 3.2% yield. Elemental analysis calcd (%) for C 64 H 60 N 22 O 17 Co(=(C 22 H 12 N 9 )(Co)(CH 3 OH) 2 (C 6 H 5 NO 2 ) 2.5 (NO 3 )(H 2 O)): C, 51.80; H, 3.49; N, 19.87. Found: C, 51.75; H, 3.31; N, 19.91. X-ray crystallographic data for K + TPHAP : C 23 H 16 KN 9 O, Mr = 473.55, crystal dimensions 0.16 0.16 0.16 mm 3, tetragonal, space group P4 2 /n, a = 20.822(2), b = 20.822(2), c = 9.635(1) Å, V = 4177.1(6) Å 3, Z = 8, calcd = 1.506 g cm 3, = 2.94 cm 1, T = 173 C, 6324 unique reflections out of 8203 with I > 2 (I), 359 parameters, 1.38 < < 33.51 o, final R factors R 1 = 0.0492 and wr 2 = 0.1424, GOF = 1.049. S3
X-ray Crystallographic data for [Co(TPHAP ) 2 (CH 3 OH) 2 (H 2 O)] 3C 6 H 5 NO 2 HNO 3 5H 2 O (TPHAP-Co Kin ): C 57.28 H 35 N 19.32 O 13.68 Co, M r = 1271.62, crystal dimensions 0.18 0.09 0.03 mm 3, Orthorhombic, space group Pca2 1, a = 29.0224(5), b = 8.4172(1), c = 27.4938(4) Å, V = 6716.4(2) Å 3, Z = 4, calcd = 1.258 g cm 3, = 3.28 cm 1, T = 183 C, 13339 unique reflections out of 20585 with I > 2 (I), 950 parameters, 1.98 < < 29.90 o, final R factors R 1 = 0.0697 and wr 2 = 0.1793, GOF = 0.998. X-ray Crystallographic data for [Co(NO 3 )(TPHAP )(CH 3 OH) 2 ] CH 3 OH C 6 H 5 NO 2 2HNO 3 H 2 O (TPHAP-Co Therm -1): C 54 H 412 N 21 O 13 Co 2, M r = 1309.94, crystal dimensions 0.17 0.08 0.04 mm 3, Orthorhombic, space group Pnc2, a = 14.6913(3), b = 27.1030(5), c = 8.2799(1) Å, V = 3296.9(1) Å 3, Z = 2, calcd = 1.320 g cm 3, = 5.76 cm 1, T = 183 C, 9066 unique reflections out of 12312 with I > 2 (I), 481 parameters, 1.98 < < 32.37 o, final R factors R 1 = 0.0722 and wr 2 = 0.1940, GOF = 1.102. X-ray Crystallographic data for [Co(NO 3 )(TPHAP )(CH 3 OH)] CH 3 OH 2.5(C 6 H 5 NO 2 ) H 2 O (TPHAP-Co Therm -2): C 35.25 H 24 N 11.75 O 9.875 Co, M r = 827.09, crystal dimensions 0.17 0.08 0.04 mm 3, monoclinic, space group P2 1 /n, a = 13.6756(3), b = 21.2490(3), c = 15.3455(3) Å, V = 4012.3(1) Å 3, Z = 4, calcd = 1.369 g cm 3, = 4.96 cm 1, T = 183 C, 7919 unique reflections out of 13657 with I > 2 (I), 891 parameters, 2.45 < < 31.30 o, final R factors R 1 = 0.0777 and wr 2 = 0.2127, GOF = 0.961. CCDC 885671 (K + TPHAP ), 885673 (TPHAP-Co Kin ), 885674 (TPHAP-Co Therm -1) and 885675 (TPHAP-Co Therm -2) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. S4
Fig. S1 ORTEP view of K + TPHAP CH 3 OH at 50% probability. A methanol molecule is coordinating K + as a crystal solvent. C, H: white, N: blue, O: red, K: purple. Fig. S2 The N HO type hydrogen bonding interactions in a pore of TPHAP-Co Kin. distances are 2.824 Å (green), 3.010 Å (blue), 2.945 (red) Å, 2.941 (pink) Å, 3.031 (orange) Å. The N O S5
Fig. S3 The N HO type hydrogen bonding interactions in a pore of TPHAP-Co Therm -1. The N O distances are 3.343 Å (red), 3.272 Å (sky blue). Fig. S4 AFM images of the surface of single crystal Co-TPHAP Kin : a) immediately after shaking the crystallization tube, b) after 5 min, c) after 10 min. Scan area 10 m 10 m. S6
Fig. S5 The bond lengths of HAP skeletons in TPHAP-Co Kin in units of Å. Bidentate TPHAP Monodentate TPHAP C6 N4 1.348(4) C20 N5 1.349(4) C28 N13 1.336(5) C42 N14 1.349(4) C6 N5 1.343(4) C20 N6 1.361(4) C28 N14 1.345(5) C42 N15 1.341(4) C12 N6 1.346(4) C22 N7 1.357(4) C34 N15 1.339(5) C44 N16 1.357(5) C12 N7 1.349(4) C22 N8 1.348(4) C34 N16 1.339(5) C44 N17 1.359(5) C18 N8 1.345(4) C19 C21 1.384(5) C40 N17 1.334(5) C41 C43 1.410(4) C18 N9 1.348(4) C20 C21 1.405(4) C40 N18 1.356(5) C42 C43 1.416(5) C19 N4 1.357(4) C21 C22 1.411(4) C41 N13 1.358(4) C43 C44 1.385(5) C19 N9 1.352(4) C41 N18 1.333(5) Fig. S6 Å. The bond lengths of HAP skeletons in TPHAP-Co Themo -1 and TPHAP-Co Themo -2 in units of TPHAP-Co Themo -1 TPHAP-Co Themo -2 C6 N4 1.344(4) C20 N5 1.348(4) C6 N4 1.340(4) C20 N5 1.351(3) C6 N5 1.338(4) C20 N6 1.363(4) C6 N5 1.337(3) C20 N6 1.358(3) C12 N6 1.339(4) C22 N7 1.355(4) C12 N6 1.333(3) C22 N7 1.360(3) C12 N7 1.352(4) C22 N8 1.347(3) C12 N7 1.347(3) C22 N8 1.350(3) C18 N8 1.346(4) C19 C21 1.403(4) C18 N8 1.347(3) C19 C21 1.407(3) C18 N9 1.347(4) C20 C21 1.396(4) C18 N9 1.339(3) C20 C21 1.402(4) C19 N4 1.343(4) C21 C22 1.406(4) C19 N4 1.357(3) C21 C22 1.400(3) C19 N9 1.351(3) C19 N9 1.352(4) S7
Fig. S7 IR spectrum of K + TPHAP. C=N stretching vibration is observed at 1593 cm 1. Fig. S8 The face index of TPHAP-Co Kin crystal and the model picture of the crystal clipping by (0 1 2) (blue) and (0 1 1) (red) plane. S8
Fig. S9. The crystal structure of TPHAP-Co Therm -2. a) From a axis with H-bonding interactions. N O distances are 2.784 Å (black broken line). b) From c axis. Fig. S10. Temperature dependent X-ray diffraction change of TPHAP-Co Therm -1. The powder plots were obtained by integration of CCD 2D-image data. Simulated powder diffraction: dotted line, TPHAP-Co Therm -1; dashed line, TPHAP-Co Therm -2. S9
Fig. S11. The simulated void spaces of TPHAP-Co systems using contact surface calculated on Mercury 3.0. TPHAP-Co Kim, 43.0% (2885.83 Å 3 ), cavity dimension: 7.4 Å 10.3 Å; TPHAP-Co Therm -1, 30.0% (988.93 Å 3 ), cavity dimension: 4.9 Å 7.4 Å; TPHAP-Co Therm -2, 47.8% (1916.75 Å 3 ), cavity dimension: 11.3 Å 2.4 Å. Probe size: 1.2 Å. S10
Electronic Supplementary Material (ESI) for Chemical Communications Fig. S12. The CCD 2D-images of TPHAP-CoKin crystals and the capillary pictures before and after in situ study. S11
Reference S1) A. P. Hammersley, FIT2D V12.012 Reference manual V6.0, Proceedings of the ESRF International Report No. ESRF98HA01T, ESRF, Grenoble, 2004. S12