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Electronic Supplementary Information
Relationship Between Crystal Structures and Photochromic Properties
of N-Salicylideneaminopyridine Derivatives
Haruki Sugiyamaa and Hidehiro Uekusab
a Department of Chemistry and Materials Science, Graduate School of Science,
Tokyo Institute of Technology, 2-12-1, Ookayama, Meguro, Tokyo 152-8551,
Japan.
b Department of Chemistry, Graduate School of Science, Tokyo Institute of
Technology, 2-12-1, Ookayama, Meguro, Tokyo 152-8551, Japan. Email:
θ range for data collection 3.602 to 27.475° 3.588 to 68.211° 3.305 to 27.476° 3.769 to 68.198°index ranges -18 ≤ h ≤ 18 -7 ≤ h ≤ 7 -53 ≤ h ≤ 54 -15 ≤ h ≤ 15
-6 ≤ k ≤ 6 -8 ≤ k ≤ 8 -31 ≤ k ≤ 32 -8 ≤ k ≤ 8 -19 ≤ l ≤ 19 -14 ≤ l ≤ 15 -6 ≤ l ≤ 6 -14 ≤ l ≤ 14
reflns collected 10577 6023 12219 6505indep reflns 2453 1988 2798 1762Rint 0.0328 0.0657 0.0680 0.0405completeness to θ 99.8 % 98.1 % 99.8 % 97.4 %abs correction Semi-empirical from equivalentsmax and min transm 0.982 and 0.821 0.962 and 0.721 0.993 and 0.411 0.976 and 0.774refinement meth Full-matrix least-squares on F2
θ range for data collection 3.332 to 27.480° 3.380 to 68.135° 3.759 to 68.215°index ranges -6 ≤ h ≤ 7 -29 ≤ h ≤ 30 -17 ≤ h ≤ 17
-24 ≤ k ≤ 24 -4 ≤ k ≤ 4 -5 ≤ k ≤ 5 -20 ≤ l ≤ 20 -41 ≤ l ≤ 41 -22 ≤ l ≤ 22
reflns collected 17821 11218 12010indep reflns 8298 2131 2256 Rint 0.0566 0.0959 0.0865completeness to θ 99.7 % 99.9 % 99.8 %abs correction Semi-empirical from equivalentsmax and min transm 0.996 and 0.196 0.783 and 0.513 0.532 and 0.336refinement meth Full-matrix least-squares on F2
data / restraints / params 8298 / 181 / 491 2131 / 0 / 154 2256 / 0 / 155goodness-of-fit on F2 1.030 1.097 1.038final R indices [I > 2σ(I)] R1 = 0.0686 R1 = 0.0455 R1 = 0.0384
θ range for data collection 5.131 to 68.264° 2.982 to 68.235° 3.023 to 27.426° 3.184 to 27.431°index ranges -38 ≤ h ≤ 38 -4 ≤ h ≤ 4 -4 2≤ h ≤ 42 -11 ≤ h ≤ 11
-7 ≤ k ≤ 7 -24 ≤ k ≤ 24 -6 ≤ k ≤ 8 -14 ≤ k ≤ 14-21 ≤ l ≤ 21 -25 ≤ l ≤ 25 -23 ≤ l ≤ 23 -14 ≤ l ≤ 14
reflns collected 18693 15638 16182 8609indep reflns 3128 3090 4063 3953Rint 0.0651 0.0542 0.0365 0.0758completeness to θ 99.8 % 99.9 % 99.8 % 99.7 %abs correction Semi-empirical from equivalentsmax and min transm 0.903 and 0.687 0.894 and 0.773 0.801 and 0.475 0.931 and 0.455refinement meth Full-matrix least-squares on F2
θ range for data collection 3.785 to 68.250° 3.179 to 68.250° 3.043 to 27.367° 3.219 to 27.415°index ranges -9 ≤ h ≤ 9 -33 ≤ h ≤ 33 -42 ≤ h ≤ 42 -48 ≤ h ≤ 47
-14 ≤ k ≤ 14 -4 ≤ k ≤ 4 -8 ≤ k ≤ 6 -9 ≤ k ≤ 9-15 ≤ l ≤ 15 -33 ≤ l ≤ 33 -23 ≤ l ≤ 23 -9 ≤ l ≤ 9
reflns collected 13821 19294 16488 10066indep reflns 7248 3386 4021 4666Rint 0.0299 0.1032 0.0458 0.0663completeness to θ 98.4 % 99.7 % 99.8 % 99.7 %abs correction Semi-empirical from equivalentsmax and min transm 0.860 and 0.733 0.893 and 0.578 0.981 and 0.603 0.925 and 0.52refinement meth Full-matrix least-squares on F2
θ range for data collection 3.928 to 68.224°. 3.107 to 25.350°. 1.198 to 27.026°.index ranges -40 ≤ h ≤ 40, , -45 ≤ h ≤ 45 -8 ≤ h ≤ 8
-8 ≤ k ≤ 8 -8 ≤ k ≤ 8 -83 ≤ k ≤ 83-7 ≤ l ≤ 6 -7 ≤ l ≤ 7 -8 ≤ l ≤ 8
reflns collected 12885 12155 16830indep reflns 2584 2976 3207 Rint 0.0570 0.0837 0.0634completeness to θ 98.0 % 99.5 % 99.6 %abs correction Semi-empirical from equivalentsmax and min transm 0.683 and 0.536 0.917 and 0.433 0.867 and 0.419refinement meth Full-matrix least-squares on F2
data / restraints / params 2584 / 0 / 181 2976 / 0 / 208 3207 / 0 / 185goodness-of-fit on F2 1.094 1.050 1.060final R indices [I > 2σ(I)] R1 = 0.0316 R1 = 0.0377 R1 = 0.0294
Figure S1: UV-Vis. spectra [before (blue line) and after (red line) UV irradiation, and after visible light exposure to colored sample (green line)] of SAP derivatives, SAP1-
SAP8.
SAP1 SAP2
SAP3 SAP4
SAP5_III SAP6 SAP3 SAP4
SAP7 SAP8
SAP9 SAP10
SAP11 SAP12
MSAP1 MSAP2 SAP3 SAP4
MSAP3
Figure S2: UV-Vis. spectra [before (blue line) and after (red line) UV irradiation, and after visible light exposure to colored sample (green line)] of SAP
derivatives, SAP9-MSAP3.
2c 3a
3b 3c
3d 3e SAP3 SAP4
3f 12g
Figure S3: UV-Vis. spectra [before (blue line) and after (red line) UV irradiation, and after visible light exposure to colored sample (green line)] of co-crystals,
3a-12g
3h 3i
3j
Figure S4: UV-Vis. spectra [before (blue line) and after (red line) UV irradiation, and after visible light exposure to colored sample (green line)] of co-crystals,
3h-3j
Figure S5: Chain motif along a-axis via intermolecular hydrogen bonding in the crystal structure of SAP9.
Figure S6: Crystal and molecular structure of 3b.
Figure S7: Crystal and molecular structure of 3c.
Figure S8: Crystal structure of 3d: (a) molecular structure of 3d; (b) intermolecular hydrogen bonds; (c) two-dimensional sheet-like structure.
Figure S9: Crystal structure of 3e: (a) molecular packing of 3e; (b) two-dimensional sheet-like structure by intermolecular hydrogen bonding.
Figure S9:(c) Crystal and molecular structure of 3e.
Fig.2- 1Figure S10: Crystal and molecular structure of 2c.
Figure S11: Crystal and molecular structure of 12g.
Figure S12: Halogen-halogen interaction in the crystal structure of 3h.
Figure S13: Crystal structure of 3i: (a) intermolecular interaction and molecular structure of 3i; (b) SAP and co-former molecules were arranged
alternately via two different types of intermolecular interaction in the crystal structure.
Figure S14: Crystal structure of 3j: (a) intermolecular interaction and molecular structure; (b) SAP molecules and co-formers were arranged alternately via
two different types of intermolecular interaction in the crystal structure.
Figure S15: SA derivatives were also known to be thermochromic organic compounds.23 As the temperature is lowered to 77 K, the crystal color changed from orange or yellow to pale yellow or colorless, respectively, because of the cis-keto to enol isomerization of SA. These pictures were taken at 296K (left) and at 77K (right).
Figure S16: Structural factors and photochromic properties: (a) dihedral angle(°); combination plot: (b) Dihedral angle / Vfree and (c) Dihedral angle / packing index. Non-photochromic [blue] and photochromic [orange] crystals for SAP derivative [circle] and co-crystals [triangle] and recently reported SA related crystals [diamond: ref. 22], [bar:
ref. 18], [square: ref. 19] and [small square: ref. 21]. The list in Table S3 includes all the SAP structures from the past study and present study.