Piezochromic Topology Switch in a Coordination Polymer

Transcription

1 Piezochromic Topology Switch in a Coordination Polymer Michał Andrzejewski, Andrzej Katrusiak* Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, Poznan, Poland *Corresponding author: katran@amu.edu.pl

2 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.

3 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.

4 Figure S4. Unit-cell parameters of CoCl 2 bpp as a function of pressure.

5 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 [%] [%] [%]

6 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 T (K) Formula weight Wavelength (Å) 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 (10) (2) (2) (2) 5.081(3) (3) 10.42(3) 93.81(13) (9) (2) 10.35(2) 93.08(6) (7) (16) (20) 92.99(5) (9) (18) 10.27(2) 93.22(6) (6) (16) (16) 93.22(5) (8) (12) (3) 92.90(3) (12) (2) (8) (2) (3) 10.71(3) 90 Volume (Å 3 ) (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 / / / / / / / / / 0.25 Calculated density (g/cm 3 ) Absorption coefficient (mm -1 ) F(000) Crystal size (mm) 0.18x0.15x x0.15x x0.15x x0.15x x0.15x x0.15x x0.15x x0.14x x0.14x0.07 θ-range for data collection ( ) 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 Rint Completeness (%) Data/ parameters/restrains 1525 / 0 / / 66 / / 66 / / 66 / / 48 / / 48 / / 48 / / 36 / / 36 / 51 Goodness-of-fit on F Final R1/wR2 (I>2σ1) / / / / / / / / / R1/wR2 (all data) / / / / / / / / / Weighting parameters w 1,w / / / / / / / / / Largest diff. peak/hole (e.å-3) 0.28 / / / / / / / / / -0.52

7 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) T (K) Formula weight Wavelength (Å) 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 (17) (13) (6) 90.14(4), 84.13(5), (13) 3.632(4) (18) (9) 90.05(4), 84.07(9), 90.03(3) (1) (2) (2) (2) (1) (3) (2) (2) (1) (2) (2) (2) (1) (3) (2) (2) (2) (4) (3) (2) Volume (Å 3 ) 565.1(5) 564.4(7) (2) (3) (2) (2) (4) Z/Z 2 / 1 2 / 1 2 / / / / / 0.5 Calculated density (g/cm 3 ) Absorption coefficient (mm -1 ) F(000) Crystal size (mm) 0.13x0.12x x0.12x x0.15x x0.15x x0.15x x0.15x x0.15x0.2 θ-range for data collection ( ) 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/ / / / / / 1429 Rint Completeness (%) Data/ parameters/restrains 646/0/36 668/9/ / 0 / / 0 / / 0 / / 0 / / 0 / 118 Goodness-of-fit on F Final R1/wR2 (I>2σ1) / / / / / / / R1/wR2 (all data) / / / / / / / Weighting parameters w 1,w / / / , , , , Largest diff. peak/hole (e.å-3) 1.88 / / / / / / / -0.44

8 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 (2) (15) (8) (7) (9) 3.414(3) (3) (9) (3) 2.007(8) 2.262(16) 2.227(8) 3.987(18) 3.394(11) 125.3(4) 115.5(6) (2) 2.016(9) 2.257(15) 2.251(10) 4.05(2) 3.406(16) 128.0(3) 115.3(6) (16) 2.012(9) 2.237(14) 2.225(10) 4.02(2) 3.398(15) 128.4(3) 115.2(6) (18) 2.024(5) 2.259(10) 2.258(6) 4.098(13) 3.412(8) 130.3(2) 114.9(3) (16) 2.021(5) 2.255(9) 2.251(5) 4.101(12) 3.422(8) 131.0(2) 115.7(3) (12) 2.017(6) 2.237(11) 2.238(8) 4.075(14) 3.43(1) 131.1(2) 116.5(4) (2) 2.151(5) 2.238(5) 2.238(5) 3.945(6) 3.774(3) (3) (5) (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) (2) (1) (1) (9) 4.187(6) 5.058(4) (8) 3.68(2) 109.6(6) 5.081(3) 5.081(3) 4.942(9) 4.096(6) 4.942(5) (8) 3.63(3) 109.0(8) (9) (9) 4.909(6) 4.014(5) 4.909(4) (8) 3.59(3) 108.9(8) (7) (7) 4.864(6) 3.939(5) 4.865(6) (5) 3.502(15) 111.8(4) (9) (9) 4.803(5) 3.936(4) 4.803(5) (5) 3.474(13) 111.4(4) (6) (6) 4.758(4) 3.892(5) 4.758(6) (7) 3.41(2) 111.8(6) (8) (8) 4.720(7) 3.825(6) 4.721(5) (6) 3.430(2) (6) 4.050(3) 4.050(6) 3.726(6) 3.584(5) 3.584(5) (3) 3.1(3) (7) 4.033(2) 4.033(2) 3.424(18) 3.577(4) 3.492(5)

9 9

10 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

11 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) (2) 1+x,y,z 11

12 C2(H2) Cl(1)* 3.090(2) 2.698(2) (11) -x,1-y,1-z C8(H8a) Cl(1)* 3.607(6) 2.672(7) (3) -x,1-y,1-z C8(H8b) Cl(1)* 3.607(14) 2.628(3) (5) -x,1-y,1-z C10*(H10)* Cl(1) 2.853(3) 2.475(2) (2) 1+x,1+y,z C5(H5) Cl(2)* 3.127(6) 2.379(12) (13) -1+x,y,z C6(H6) Cl(2)* 3.869(2) 2.917(4) (3) -x,1-y,-z 2.57 C1*(H1)* Cl(1) 3.082(2) 2.682(2) (2) 1+x,y,z C2(H2) Cl(1)* 3.093(3) 2.703(3) (13) -x,1-y,1-z C8(H8a) Cl(1)* 3.605(12) 2.671(12) (2) -x,1-y,1-z C8(H8b) Cl(1)* 3.623(14) 2.652(3) (12) -x,1-y,1-z C10*(H10)* Cl(1) 2.863(3) 2.471(14) (4) 1+x,1+y,z C5(H5) Cl(2)* 3.111(2) 2.322(10) (2) -1+x,y,z C6(H6) Cl(2)* 3.853(14) 2.813(3) (13) -x,1-y,-z 12