Piezochromic Topology Switch in a Coordination Polymer Michał Andrzejewski, Andrzej Katrusiak* Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznan, Poland *Corresponding author: katran@amu.edu.pl
Figure S1. The single crystal of CoCl 2 bpp compressed in a diamond-anvil cell, pressure values (in GPa) were placed in the left side of pictures.
Figure S2. CoCl 2 bpp VIS spectra in the function of pressure up to 3.5 GPa. Figure S3. The spectrum of CoCl2bpp phases divided into Δλ ranges for integrating the signal, cf. Table S1.
Figure S4. Unit-cell parameters of CoCl 2 bpp as a function of pressure.
Table S1. Integrated signal Integrated signal α to β α to γ β to γ Wavelength phase phase phase change change change threshold [nm] α β γ [%] [%] [%] 475-700 60.30 50.71 13.29-15.90-77.96-73.79 700-800 0.37 0.74 0.52 100 40.5-29.73 600-700 28.47 23.41 4.15-17.77-85.42-82.27 500-600 30.31 23.76 7.72-21.61-74.53-67.51 400-500 4.15 9.77 3.99 135.4-3.86-59.16 750-800 0.08 0.13 0.11 62.5 37.5-15.38 700-750 0.44 0.61 0.41 38.6-6.81-32.78 650-700 10.18 8.25 2.58-18.95-85.56-82.18 600-650 18.64 15.45 2.72-17.11-85.41-82.39 550-600 17.97 12.47 3.04-30.61-83.08-75.62 500-550 12.65 11.55 4.77-8.69-62.29-58.70 450-500 3.44 6.55 2.37 90-31.1-63.81 400-450 0.73 3.31 1.64 353 124.65-50.46
Table S2. Detailed crystallographic data of Co 2 Cl 2 dpp studies in the function of pressure and temperature. Phase α α α α α α α β β Formula C 13H 14N 2Cl 2Co C 13H 14N 2Cl 2Co C 13H 14N 2Cl 2Co C 13H 14N 2Cl 2Co C 13H 14N 2Cl 2Co C 13H 14N 2Cl 2Co C 13H 14N 2Cl 2Co C 13H 14N 2Cl 2Co C 13H 14N 2Cl 2Co p (GPa) 0.1 MPa 0.29 0.65 0.99 1.21 1.51 1.76 2.10 2.26 T (K) 296 296 296 296 296 296 296 296 296 Formula weight 328.09 328.09 328.09 328.09 328.09 328.09 328.09 328.09 328.09 Wavelength (Å) 1.54050 0.71073 0.71073 0.71073 0.71073 0.71073 0.71073 0.71073 0.71073 Crystal system Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Orthorhombic Orthorhombic Space group P2 1/m P2 1/m P2 1/m P2 1/m P2 1/m P2 1/m P2 1/m Pnmm Pnmm a b c β 5.19360(10) 12.9884(2) 10.4964(2) 93.579(2) 5.081(3) 12.910(3) 10.42(3) 93.81(13) 4.9634(9) 12.890(2) 10.35(2) 93.08(6) 4.8877(7) 12.8911(16) 10.282(20) 92.99(5) 4.8116(9) 12.8538(18) 10.27(2) 93.22(6) 4.7442(6) 12.8597(16) 10.233(16) 93.22(5) 4.6845(8) 12.8898(12) 10.167(3) 92.90(3) 4.0498(12) 13.587(2) 10.801(8) 90 4.033(2) 13.632(3) 10.71(3) 90 Volume (Å 3 ) 706.67(2) 681.9(18) 661.4(16) 646.9(12) 634.3(13) 623.3(10) 613.1(2) 594.3(5) 588.8(15) Z/Z 2 / 0.5 2 / 0.5 2 / 0.5 2 / 0.5 2 / 0.5 2 / 0.5 2 / 0.5 2 / 0.25 2 / 0.25 Calculated density (g/cm 3 ) 1.542 1.598 1.647 1.684 1.718 1.748 1.777 1.833 1.850 Absorption coefficient (mm -1 ) 12.850 1.632 1.682 1.720 1.754 1.785 1.815 1.872 1.890 F(000) 334 334 334 334 334 334 334 334 334 Crystal size (mm) 0.18x0.15x0.07 0.18x0.15x0.07 0.18x0.15x0.07 0.18x0.15x0.07 0.18x0.15x0.07 0.18x0.15x0.07 0.18x0.15x0.07 0.15x0.14x0.07 0.15x0.14x0.07 θ-range for data collection ( ) 8.44 149.84 8.04 53.426 9.834 52.766 9.96 52.64 7.482 56.946 7.488 56.94 7.49 56.824 9.76 57.374 9.746 55.438 Min/max indices:h, k, l -6/5, -16/16, -13/13-5/5, -16/15, -6/6-6/6, -15/15, -4/4-6/6, -15/15, -4/4-6/6, -16/17, -4/4-6/6, -16/17, -4/4-6/6, -16/17, -4/4-5/5, -18/17, -4/4-5/5, -17/18, -4/4 Reflect. Collected/unique 12451 1350 3526 3453 4388 4244 4124 3825 3093 Rint 0.0168 0.0544 0.1092 0.0953 0.0685 0.0787 0.0769 0.1236 0.1072 Completeness (%) 99.61 23.04 27.54 28.03 27.06 27.61 26.29 38.64 37.18 Data/ parameters/restrains 1525 / 0 / 118 347 / 66 / 88 388 / 66 / 88 382 / 66 / 88 454 / 48 / 88 457 / 48 / 88 422 / 48 / 88 323 / 36 / 51 290 / 36 / 51 Goodness-of-fit on F2 1.086 1.092 1.143 1.126 1.050 1.132 1.175 1.100 1.086 Final R1/wR2 (I>2σ1) 0.0279 / 0.0738 0.0483 / 0.0439 0.0501 / 0.0930 0.0648 / 0.1194 0.0423 / 0.0769 0.0405 / 0.0729 0.0502 / 0.0746 0.0829 / 0.2003 0.0861 / 0.1992 R1/wR2 (all data) 0.0312 / 0.0759 0.1294 / 0.0584 0.1054 / 0.1118 0.1055 / 0.1387 0.0784 / 0.0895 0.0945 / 0.0853 0.1184 / 0.0902 0.1481 / 0.2440 0.1384 / 0.2383 Weighting parameters w 1,w 2 0.045 / 0.075 0.007 / 0.000 0.050 / 0.067 0.045 / 2.705 0.045 / 0.243 0.034 / 0.081 0.023 / 0.819 0.152 / 0 0.117 / 3.377 Largest diff. peak/hole (e.å-3) 0.28 / -0.21 0.24 / -0.28 0.26 / -0.17 0.36 / -0.24 0.17 / -0.16 0.19 / -0.18 0.17 / -0.18 0.64 / -0.45 0.61 / -0.52
Table S2. Continued. Phase γ γ α α α α α Formula C 13H 14N 2Cl 2Co C 13H 14N 2Cl 2Co C 13H 14N 2Cl 2Co C 13H 14N 2Cl 2Co C 13H 14N 2Cl 2Co C 13H 14N 2Cl 2Co C 13H 14N 2Cl 2Co p (Gpa) 2.51 2.61 0.0001 0.0001 0.0001 0.0001 0.0001 T (K) 296 296 296 273 200 150 100 Formula weight 328.09 328.09 328.09 328.09 328.09 328.09 328.09 Wavelength (Å) 0.71073 0.71073 1.54050 1.54050 1.54050 1.54050 1.54050 Crystal system Triclinic Triclinic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Space group P-1 P-1 P2 1/m P2 1/m P2 1/m P2 1/m P2 1/m a b c α, β, γ 3.6356(17) 14.5440(13) 10.744(6) 90.14(4), 84.13(5), 90.014(13) 3.632(4) 14.5490(18) 10.740(9) 90.05(4), 84.07(9), 90.03(3) 5.1936(1) 12.9884(2) 10.4964(2) 93.579(2) 5.1799(1) 12.9774(3) 10.4866(2) 93.567(2) 5.1464(1) 12.9530(2) 10.4646(2) 93.524(2) 5.1250(1) 12.9420(3) 10.4448(2) 93.466(2) 5.1067(2) 12.9269(4) 10.4264(3) 93.435(2) Volume (Å 3 ) 565.1(5) 564.4(7) 706.67(2) 703.56(3) 696.26(2) 691.51(2) 687.05(4) Z/Z 2 / 1 2 / 1 2 / 0.5 2 / 0.5 2 / 0.5 2 / 0.5 2 / 0.5 Calculated density (g/cm 3 ) 1.932 1.931 1.542 1.549 1.565 1.576 1.586 Absorption coefficient (mm -1 ) 1.969 1.971 12.850 12.907 13.042 13.132 13.217 F(000) 334 334 334 334 334 334 334 Crystal size (mm) 0.13x0.12x0.07 0.13x0.12x0.07 0.18x0.15x0.07 0.1x0.15x0.2 0.1x0.15x0.2 0.1x0.15x0.2 0.1x0.15x0.2 θ-range for data collection ( ) 6.77 56.5 6.774 56.16 8.44 149.84 8.44 146.72 8.46 146.7 8.48 146.26 8.48 146.26 Min/max indices:h, k, l -4/4, -19/19, -4/4-4/4, -19/19, -6/6-6/5, -16/16, -13/13-6/6, -13/15, -12/12-6/6, -13/15, -12/12-6/6, -13/15, -12/12-6/6, -13/15, -12/12 Reflect. Collected/unique 3777/646 3781/668 12451 5761 / 1459 5643 / 1449 5566 / 1441 5418 / 1429 Rint 0.1510 0.1984 0.0168 0.0296 0.0290 0.0315 0.0333 Completeness (%) 23.21 24.51 99.61 98.51 98.50 98.63 98.15 Data/ parameters/restrains 646/0/36 668/9/37 1525 / 0 / 118 1459 / 0 / 118 1449 / 0 / 118 1441 / 0 / 118 1429 / 0 / 118 Goodness-of-fit on F2 2.382 1.931 1.086 1.041 1.049 1.060 1.119 Final R1/wR2 (I>2σ1) 0.3655 / 0.6932 0.2973 / 0.5797 0.0279 / 0.0738 0.0300 / 0.0768 0.0296 / 0.0765 0.0311 / 0.0798 0.0349 / 0.0946 R1/wR2 (all data) 0.4393 / 0.7199 0.3974 / 0.6328 0.0312 / 0.0759 0.0324 / 0.0787 0.0310 / 0.0778 0.0322 / 0.0808 0.0360 / 0.0954 Weighting parameters w 1,w 2 0.2 / 0 0.2 / 0 0.045 / 0.075 0.044, 0.126 0.042, 0.303 0.045, 0.360 0.051, 0.607 Largest diff. peak/hole (e.å-3) 1.88 / -1.01 1.61 / -1.18 0.28 / -0.21 0.30 / -0.25 0.38 / -0.231 0.56 / -0.31 0.74 / -0.44
Table S3. Dimensions of coordination polyhedron around Co. Pressure [GPa] Co Co Co N(bpp) Co Cl(1) Co Cl(2) Cl(1) Cl(2) N(1) N(1) Cl(1) Co Cl(2) N(1) Co N(1) [Å] [Å] [Å] [Å] [Å] [Å] [ ] [ ] 0.1 MPa 12.9884(2) 2.0414(15) 2.2410(8) 2.2543(7) 3.9996(9) 3.414(3) 125.67(3) 113.51(9) 0.29 12.910(3) 2.007(8) 2.262(16) 2.227(8) 3.987(18) 3.394(11) 125.3(4) 115.5(6) 0.65 12.890(2) 2.016(9) 2.257(15) 2.251(10) 4.05(2) 3.406(16) 128.0(3) 115.3(6) 0.99 12.8911(16) 2.012(9) 2.237(14) 2.225(10) 4.02(2) 3.398(15) 128.4(3) 115.2(6) 1.21 12.8538(18) 2.024(5) 2.259(10) 2.258(6) 4.098(13) 3.412(8) 130.3(2) 114.9(3) 1.51 12.8597(16) 2.021(5) 2.255(9) 2.251(5) 4.101(12) 3.422(8) 131.0(2) 115.7(3) 1.76 12.8898(12) 2.017(6) 2.237(11) 2.238(8) 4.075(14) 3.43(1) 131.1(2) 116.5(4) 2.10 13.587(2) 2.151(5) 2.238(5) 2.238(5) 3.945(6) 3.774(3) 123.62(3) 132.78(5) 2.26 13.631(3) 2.042(6) 2.270(6) 2.179(6) 3.888(4) 3.746(9) 121.5(7) 132.3(8) Pressure [GPa] Cl H [Å] Cl C [Å] Cl H C [ ] Cl Cl* [Å] Co Co* [Å] Cl(1) N* [Å] Co(1) Cl(1)* [Å] Co(1) Cl(2)* [Å] 0.1 MPa 3.22(3) 3.750(3) 116.68(2) 5.1936(1) 5.1936(1) 5.0578(9) 4.187(6) 5.058(4) 0.29 3.243(8) 3.68(2) 109.6(6) 5.081(3) 5.081(3) 4.942(9) 4.096(6) 4.942(5) 0.65 3.196(8) 3.63(3) 109.0(8) 4.9634(9) 4.9634(9) 4.909(6) 4.014(5) 4.909(4) 0.99 3.159(8) 3.59(3) 108.9(8) 4.8877(7) 4.8877(7) 4.864(6) 3.939(5) 4.865(6) 1.21 3.024(5) 3.502(15) 111.8(4) 4.8116(9) 4.8116(9) 4.803(5) 3.936(4) 4.803(5) 1.51 3.000(5) 3.474(13) 111.4(4) 4.7442(6) 4.7442(6) 4.758(4) 3.892(5) 4.758(6) 1.76 2.927(7) 3.41(2) 111.8(6) 4.6845(8) 4.6845(8) 4.720(7) 3.825(6) 4.721(5) 2.10 2.723(6) 3.430(2) 130.09(6) 4.050(3) 4.050(6) 3.726(6) 3.584(5) 3.584(5) 2.26 2.26(3) 3.1(3) 142.61(7) 4.033(2) 4.033(2) 3.424(18) 3.577(4) 3.492(5)
9
Figure S5. CH Cl hydrogen bonds in CoCl 2 bpp (in green), their distances were listed below in table S4; donoring and accepting atom names were inset. Figure S6. Diffusion method used in a synthesis of CoCl 2 bpp. Figure S7. Shortest non-bonding CH Cl contacts in CoCl 2 bpp structures as a function of pressure. 10
Table S4. The geometry of CH Cl hydrogen bonds in CoCl 2 bpp in the function of pressure. Contacts above the sum of van der Waals radii were listed in red. Pressure [GPa] D A [Å] H A [Å] DH A [ ] symmetry code (*) 0.1 MPa C(2)H(2) Cl(1)* 3.562(2) 2.92(2) 129.4(18) 1+x,y,z C(7)H(7) Cl(1)* 3.780(2) 3.05(2) 135.3(19) 1+x,1.5-y,z C5(H5) Cl(2)* 3.879(2) 2.95(3) 167.0(2) 1-x,-0.5+y,2-z 0.33 C7(H7A) Cl(1)* 3.70(2) 2.949(12) 135.2(11) -x,0.5+y,1-z C(2)H(2) Cl(1)* 3.512(10) 2.796(5) 134.5(13) 1+x,1.5-y,z C5(H5) Cl(2)* 3.90(2) 2.992(7) 167.0(7) 1-x,-0.5+y,2-z 0.65 C7(H7B) Cl(1)* 3.66(2) 2.898(14) 135.8(11) -x,0.5+y,1-z C5(H5) Cl(2)* 3.84(2) 2.940(7) 163.8(9) 1-x,-0.5+y,2-z C2(H2) Cl(1)* 3.63(2) 2.820(3) 110.6(6) -1+x,y,z 0.99 C7(H7B) Cl(1)* 3.62(3) 2.872(15) 134.7(12) -x,0.5+y,1-z C5(H5) Cl(2)* 3.78(2) 2.886(7) 162.4(11) 1-x,-0.5+y,2-z C2(H2) Cl(1)* 3.440(14) 2.795(3) 127.5(11) -1+x,y,z 1.21 C7(H7B) Cl(1)* 3.577(14) 2.859(9) 131.5(6) -x,0.5+y,1-z C5(H5) Cl(2)* 3.728(13) 2.838(4) 160.4(5) 1-x,-0.5+y,2-z C2(H2) Cl(1)* 3.403(8) 2.755(2) 127.6(6) -1+x,y,z 1.51 C7(H7B) Cl(1)* 3.546(13) 2.835(8) 130.9(6) -x,0.5+y,1-z C5(H5) Cl(2)* 3.736(12) 2.844(4) 161.2(5) 1-x,-0.5+y,2-z C2(H2) Cl(1)* 3.379(7) 2.737(2) 127.0(6) -1+x,y,z C8(H8B) Cl(2)* 3.661(16) 2.927(7) 133.3(10) 1-x,-0.5+y,2-z 1.76 C7(H7B) Cl(1)* 3.497(19) 2.791(10) 130.2(8) -x,0.5+y,1-z C5(H5) Cl(2)* 3.736(12) 2.844(4) 161.2(5) 1-x,-0.5+y,2-z C2(H2) Cl(1)* 3.363(10) 2.726(4) 126.5(7) -1+x,y,z C8(H8B) Cl(2)* 3.661(16) 2.927(7) 133.3(10) 1-x,-0.5+y,2-z 2.10 C5(H5a) Cl(1)* 3.434(14) 2.726(14) 130.4(9) 1-x,0.5+y,-0.5-z C2(H2) Cl(1)* 3.50(2) 3.010(11) 114.0(3) 1+x,y,-z C10(H10) Cl(1)* 3.36(1) 2.785(11) 121.0(3) 1+x,1+y,-z 2.23 C5(H5a) Cl(1)* 3.416(17) 2.706(12) 130.4(10) 1-x,0.5+y,-0.5-z C2(H2) Cl(1)* 3.418(15) 2.868(3) 119.0(12) 1+x,y,-z C10(H10) Cl(1)* 3.84(2) 3.040(7) 145.6(11) 1+x,1+y,-z 2.51 C1*(H1)* Cl(1) 3.091(5) 2.720(4) 104.68(2) 1+x,y,z 11
C2(H2) Cl(1)* 3.090(2) 2.698(2) 164.40(11) -x,1-y,1-z C8(H8a) Cl(1)* 3.607(6) 2.672(7) 109.40(3) -x,1-y,1-z C8(H8b) Cl(1)* 3.607(14) 2.628(3) 106.38(5) -x,1-y,1-z C10*(H10)* Cl(1) 2.853(3) 2.475(2) 104.42(2) 1+x,1+y,z C5(H5) Cl(2)* 3.127(6) 2.379(12) 137.41(13) -1+x,y,z C6(H6) Cl(2)* 3.869(2) 2.917(4) 167.92(3) -x,1-y,-z 2.57 C1*(H1)* Cl(1) 3.082(2) 2.682(2) 104.52(2) 1+x,y,z C2(H2) Cl(1)* 3.093(3) 2.703(3) 163.20(13) -x,1-y,1-z C8(H8a) Cl(1)* 3.605(12) 2.671(12) 108.38(2) -x,1-y,1-z C8(H8b) Cl(1)* 3.623(14) 2.652(3) 107.31(12) -x,1-y,1-z C10*(H10)* Cl(1) 2.863(3) 2.471(14) 103.22(4) 1+x,1+y,z C5(H5) Cl(2)* 3.111(2) 2.322(10) 136.21(2) -1+x,y,z C6(H6) Cl(2)* 3.853(14) 2.813(3) 165.52(13) -x,1-y,-z 12