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Supporting Information
© Wiley-VCH 2007
69451 Weinheim, Germany
S1
Crystal-to-Crystal Transformation between Three Cu(I) Coordination Polymers and Structural Evidence for Luminescence
Thermochromism
Tae Ho Kim1, Yong Woon Shin2, Jong Hwa Jung1, Jae Sang Kim1, and Jineun Kim1*
1 Department of Chemistry (BK21) and Research Institute of Natural Science, Gyeongsang National University, Jinju 660-701, S. Korea
2 Test & Analytical Laboratory, Korea Food & Drug Administration, Busan 608-829, South Korea
Table of Contents: Title and table of contents································································ S1 General······················································································· S3 Scheme S1. Synthesis of 1,4-bis((methylthio)propanoyl)piperazine (L).··········· S3 Preparations of 1, 2, 3, and 3’ ··························································· S4 Figure S1. Ortep diagram of L. ··························································· S5 Table S1. Crystal data and structure refinement for L. ································ S5 Figure S2. Photograph of crystals 1, 2, and 3 with/without UV irradiation. ······· S6 Figure S3. SEM images of 1, 2, and 3’. ················································· S7 Figure S4. Ortep (a) and packing (b) diagrams of 1. ·································· S8 Table S2. Crystal data and structure refinement for 1.································· S9 Figure S5. Ortep (a) and packing (b) diagrams of 2. ·································· S10 Table S3. Crystal data and structure refinement for 2.································· S11 Figure S6. Ortep (a) and packing (b) diagrams of 3. ·································· S12 Table S4. Crystal data and structure refinement for 3.································· S13 Figure S7. Conformation of L. ··························································· S14 Figure S8. Packing arrangements of Cu4I4. ············································· S14 Table S4. Bond distances of 2 at four different temperatures. ························ S15 Table S5. Bond distances of 3 at four different temperatures. ························ S17 Figure S9. Photoluminescence spectra of before (a) and after (b) heating at
180 °C. ·············································································· S19
Figure S10. Powder XRD Patterns of 1.················································· S20 Figure S11. Powder XRD Patterns of 2.················································· S21
S2
Figure S12. Powder XRD Patterns of 3’ (a and b) and 3 (c).························· S22 Figrue S13. Thermogravimetric analysis (TGA) and differential thermal
analysis (DTA) traces for 1.······················································ S23 Figrue S14. Thermogravimetric analysis (TGA) and differential thermal
analysis (DTA) traces for 2.······················································ S23 Figrue S15. Thermogravimetric analysis (TGA) and differential thermal
analysis (DTA) traces for 3’.····················································· S24
S3
General The 1H and 13C NMR spectra were recorded with a Bruker Advance-300(300 MHz) NMR spectrometer.
The FT-IR spectra of the coordination polymers were measured with a Shimadzu FT-IR 8100
spectrometer. The elemental analysis was carried out on a LECO CHNS-932 elemental analyzer.
Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were performed under N2(g)
at a scan rate of 10 °C min-1 using a TA SDT Q600 thermal analyzer. For field emission scanning electron
microscope (FE-SEM) a piece of compounds was placed on a carbon tape after gold coating, the
specimen was then examined with Philips XL30 S FEG.
Scheme S1
SO
OHi ii
i. SOCl2, triethyl amineii. triethyl amine, thiomorpholine
SN
O
L
S
2-(cyclohexylthio)-1-thiomorpholinoethane (L). Thionyl chloride (2.38 g, 20.0 mmol) was added
dropwise to 2-cyclohexylthioacetic acid (3.48 g, 20.0 mmol) in the pesence of triethylamine (2.02 g, 20.0
mmol) in chloroform. The mixture was refluxed for 2 h and cooled down to room temperature. Then,
thiomorpholine (2.38 g, 20.0 mmol) and triethylamine (2.02 g, 20.0 mmol) in chloroform were added
dropwise to the resulting acid chloride solution, cooled by salt and ice water. The solution was stirred for
2 h, and then water was added. Organic layer was collected and water layer was extr
acted with chloroform. The combined organic layers dried with anhydrous sodium sulfate were
evaporated to give crude oil. Column chromatography (silica gel, ethyl acetate/hexane = 20/80 (v/v), Rf
0.2) gave pure product (4.18 g, 78%). 1H NMR (300 MHz, CDCl3): δ 3.857 (d, 4H, CH2NCH2), 3.326 (s,
2H, COCH2S), 2.805 (m, 1H SCH), 2.702 (d, 4H, CH2SCH2), 1.756 (m, 10H, CH(CH2)5). 13C NMR (75.4
MHz, CDCl3): δ 168.50, 44.33, 33.39, 32.08, 27.80, 27.39, 25.92, 25.74. IR(KBr, ν, cm-1): 2926 s, 2851 s,
1641 s, 1445 s, 1366 m, 1288 m, 1135 s, 1038 w, 999 w, 958 s, 917 m, 818 w, 738 w, 659 w. Mass
spectrum m/z 259 (M, 11 %), 145 (100), 130 (25), 117 (57), 102(15), 83 (20).
S4
Preparations of 1, 2, 3, and 3’
[Cu2I2L2]n (1): An acetonitrile (1 mL) solution of L (0.026 g, 0.10 mmol) was allowed to mix with an
acetonitrile (1 mL) solution of CuI (0.019 g , 0.10 mmol), followed by sonication. Yellowish-colored
precipitates were filtered and washed with diethyl ether/acetonitrile (1/1) solution (0.026 g, 58%). Single
crystals suitable for X-ray analysis were obtained by slow evaporation. m.p. 173-175 °C. IR(KBr, ν, cm-
1): 2931 s, 2852 s, 1660 s, 1424 s, 1367 m, 1287 m, 1177 s, 1039 w, 997 w, 956 s, 882 m, 817 w, 730 w,
649 w. [Cu2I2L2]n Anal. Calcd. for C24H42N2O2S4Cu2I2: C 32.04, H 4.70, N 3.11, S 14.25. Found: C 31.97,
H 4.66, N 3.27, S 14.39%.
[Cu4I4L2]n (2): An acetonitrile (1 mL) solution of L (0.026 g, 0.10 mmol) was allowed to mix with an
acetonitrile (1 mL) solution of CuI (0.038 g , 0.20 mmol), followed by diethyl ether diffusion and
sonication. White precipitates were filtered and washed with diethyl ether/acetonitrile (1/1) solution
(0.033 g, 52%). Single crystals suitable for X-ray analysis were obtained by diethyl ether diffusion. m.p.
202-204 °C. IR(KBr, ν, cm-1): 2921 s, 2847 m, 1642 s, 1440 s, 1364 w, 1294 m, 1253 w, 1130 w, 1044 w,
960 m, 923 w, 733 w, 651 w. [Cu4I4L2]n Anal. Calcd. for C24H42N2O2S4Cu4I4: C 22.51, H 3.31, N 2.19, S
10.02. Found: C 22.33, H 3.66, N 2.14, S 9.71%.
{[Cu4I4L2]·CH3CN·n-C6H12}n (3) An acetonitrile (1 mL) solution of L (0.026 g, 0.10 mmol) was allowed
to mix with an acetonitrile (1 mL) solution of CuI (0.038 g , 0.20 mmol), followed by diethyl ether/n-
Hexane (1/1) diffusion and sonication. White precipitates were filtered and washed with diethyl ether/n-
Hexane/acetonitrile (1/1/1) solution (0.044 g, 69%). Single crystals suitable for X-ray analysis were
obtained from boundary surface between n-hexane and acetonitrile solution (Figure S1b) .
[Cu4I4L2]n (3’): 3’ was obtained by desolvating the white precipitates 3 under vacuum for 1 hr. m.p. 176-
178 °C. IR(KBr, ν, cm-1): 2920 s, 2847 m, 1652 s, 1445 s, 1366 w, 1303 m, 1253 w, 1118 w, 1043 w, 958
m, 916 w, 729 w, 651 w. [Cu4I4L2]n Anal. Calcd. for C24H42N2O2S4Cu4I4: C 22.51, H 3.31, N 2.19, S
10.02. Found: C 22.55, H 3.46, N 2.35, S 10.29%.
S5
Figure S1. Ortep diagram of L. Table S1. Crystal data and structure refinement for L. ---------------------------------------------------------------------------------------------------------- Empirical formula C12H21NOS2 Formula weight 259.42 Temperature 173(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P2(1)/c Unit cell dimensions a = 14.0036(6) Å α= 90°. b = 9.3364(4) Å β= 94.4060(10)°. c = 10.2501(4) Å γ = 90°. Volume 1336.17(10) Å3 Z 4 Density (calculated) 1.290 g/cm3 Absorption coefficient 0.379 mm-1 F(000) 560 Crystal size 0.35 x 0.25 x 0.15 mm3 Theta range for data collection 2.62 to 28.27°. Index ranges -18<=h<=17, -11<=k<=12, -9<=l<=13 Reflections collected 8357 Independent reflections 3165 [R(int) = 0.0286] Completeness to theta = 28.27° 95.3 % Absorption correction Empirical ψ-scan Max. and min. transmission 0.2846 and 0.2228 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3165 / 0 / 145 Goodness-of-fit on F2 1.058 Final R indices [I>2sigma(I)] R1 = 0.0338, wR2 = 0.0848 R indices (all data) R1 = 0.0452, wR2 = 0.0910 Largest diff. peak and hole 0.323 and -0.245 e.Å-3 ----------------------------------------------------------------------------------------------------------
S6
Figure S2. Photograph of crystals 1, 2, and 3 with/without UV irradiation; yellow crystal 1 and white crystal 2 (top), orange luminescent 2 (bottom) (a), green luminescent 3 grown from boundary surface between n-hexane layer and acetonitrile solution (b), block crystal 2 and plate (urchin shape) crystal 3 (top), orange luminescent 2 and green luminescent 3 (bottom) (c).
(b)
(a) (c)
UV irradiation UV irradiation
S7
(a)
(b) (c) Figure S3. SEM images of 1, 2, and 3’; rhombohedron-shape block 1 (a), hexagonal-shape block 2 (b), and plate 3’ (c).
S8
(a)
(b)
Figure S4. Ortep (a) and packing (b) diagrams of 1. Hydrogen atoms are omitted.
S9
Table S2. Crystal data and structure refinement for 1. ---------------------------------------------------------------------------------------------------------- Empirical formula C12H21NOS2CuI
Formula weight 449.86
Temperature 173(2) K
Wavelength 0.71073 Å
Crystal system Monoclinic
Space group P2(1)/c
Unit cell dimensions a = 10.4687(5) Å α= 90°.
b = 8.7776(4) Å β= 103.5330(10)°.
c = 17.4451(8) Å γ = 90°.
Volume 1558.52(13) Å3
Z 4
Density (calculated) 1.917 g/cm3
Absorption coefficient 3.639 mm-1
F(000) 888
Crystal size 0.20 x 0.16 x 0.05 mm3
Theta range for data collection 2.00 to 28.32°.
Index ranges -11<=h<=13, -11<=k<=9, -22<=l<=23
Reflections collected 9544
Independent reflections 3657 [R(int) = 0.0549]
Completeness to theta = 28.32° 94.4 %
Absorption correction Empirical ψ-scan
Max. and min. transmission 0.3505 and 0.2406
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 3657 / 0 / 163
Goodness-of-fit on F2 1.024
Final R indices [I>2sigma(I)] R1 = 0.0305, wR2 = 0.0594
R indices (all data) R1 = 0.0489, wR2 = 0.0646
Largest diff. peak and hole 0.981 and -0.645 e.Å-3 ----------------------------------------------------------------------------------------------------------
S10
(a)
(b) Figure S5. Ortep (a) and packing (b) diagrams of 2. Hydrogen atoms are omitted.
S11
Table S3. Crystal data and structure refinement for 2. ---------------------------------------------------------------------------------------------------------- Empirical formula C24H42N2O2S4Cu4I4
Formula weight 1280.60
Temperature 173(2) K
Wavelength 0.71073 Å
Crystal system Orthorhombic
Space group Pbca
Unit cell dimensions a = 13.5252(6) Å α= 90°.
b = 20.7188(9) Å β= 90°.
c = 27.2475(12) Å γ = 90°.
Volume 7635.5(6) Å3
Z 8
Density (calculated) 2.228 g/cm3
Absorption coefficient 5.676 mm-1
F(000) 4864
Crystal size 0.25 x 0.18 x 0.16 mm3
Theta range for data collection 1.49 to 28.31°.
Index ranges -18<=h<=17, -18<=k<=27, -35<=l<=34
Reflections collected 46812
Independent reflections 9254 [R(int) = 0.0743]
Completeness to theta = 28.31° 97.5 %
Absorption correction Empirical ψ-scan
Max. and min. transmission 0.2967 and 0.1943
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 9254 / 0 / 361
Goodness-of-fit on F2 1.059
Final R indices [I>2sigma(I)] R1 = 0.0401, wR2 = 0.0755
R indices (all data) R1 = 0.1105, wR2 = 0.0972
Largest diff. peak and hole 0.800 and -0.885 e.Å-3 ----------------------------------------------------------------------------------------------------------
S12
(a)
(b)
Figure S6. Ortep (a) and packing (b) diagrams of 3. Hydrogen atoms and solvates are omitted.
S13
Table S4. Crystal data and structure refinement for 3. ---------------------------------------------------------------------------------------------------------- Empirical formula C32H59N3O2S4Cu4I4
Formula weight 1407.82
Temperature 173(2) K
Wavelength 0.71073 Å
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 11.3013(4) Å α= 93.8340(10)°.
b = 14.1099(4) Å β= 102.1980(10)°.
c = 15.2300(5) Å γ = 100.4750(10)°.
Volume 2320.14(13) Å3
Z 2
Density (calculated) 2.015 g/cm3
Absorption coefficient 4.680 mm-1
F(000) 1360
Crystal size 0.30 x 0.15 x 0.05 mm3
Theta range for data collection 1.38 to 28.33°.
Index ranges -14<=h<=15, -18<=k<=18, -20<=l<=20
Reflections collected 27807
Independent reflections 10810 [R(int) = 0.0431]
Completeness to theta = 28.33° 93.5 %
Absorption correction SADABS
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 10810 / 28 / 471
Goodness-of-fit on F2 1.093
Final R indices [I>2sigma(I)] R1 = 0.0424, wR2 = 0.0860
R indices (all data) R1 = 0.0786, wR2 = 0.1033
Largest diff. peak and hole 1.227 and -0.924 e.Å-3 ----------------------------------------------------------------------------------------------------------
S14
(a) (b) Figure S7. Conformation of L; Syn arrangement in 2 (a), Anti arrangement in 3 (b).
(a) (b)
(c) (d)
Figure S8. Packing arrangements of Cu4I4; view down b-axis of 2 (a), view down a-axis of 3 (b), view down c-axis of 2 (c), view down c-axis of 3 (d). All atoms of L except S are omitted for clarity.
S15
Table S5. Bond distances of 2 at four different temperatures.
Atom1 Atom2 d-123K d-173K d-223K d-298K (d-298K) -
(d-123K)
C2 C3 1.523 1.55 1.546 1.599 0.076
C14 C15 1.495 1.494 1.516 1.561 0.066
Cu1 Cu3 2.773 2.788 2.805 2.833 0.06
Cu1 Cu2 2.74 2.751 2.764 2.789 0.049
C4 C5 1.518 1.496 1.491 1.567 0.049
N1 C12 1.454 1.468 1.476 1.489 0.035
Cu2 Cu3 2.711 2.718 2.727 2.74 0.029
Cu2 Cu4 2.608 2.611 2.617 2.631 0.023
C7 C8 1.509 1.523 1.529 1.53 0.021
Cu3 I1 2.719 2.723 2.729 2.736 0.017
Cu1 I1 2.663 2.665 2.669 2.679 0.016
Cu4 I4 2.668 2.675 2.678 2.684 0.016
O2 C20 1.221 1.236 1.231 1.237 0.016
Cu3 I3 2.731 2.738 2.744 2.745 0.014
Cu3 Cu4 2.741 2.74 2.745 2.755 0.014
C16 C17 1.544 1.555 1.551 1.555 0.011
Cu2 I1 2.686 2.688 2.692 2.696 0.01
C11 C12 1.512 1.517 1.522 1.522 0.01
Cu2 I2 2.654 2.656 2.658 2.663 0.009
Cu2 I4 2.709 2.713 2.716 2.717 0.008
S1 C6 1.851 1.846 1.854 1.859 0.008
N2 C20 1.36 1.355 1.371 1.368 0.008
C13 C18 1.508 1.509 1.509 1.515 0.007
C21 C22 1.522 1.518 1.525 1.529 0.007
Cu1 I2 2.703 2.708 2.711 2.709 0.006
C9 C10 1.516 1.5 1.507 1.522 0.006
Cu1 I3 2.705 2.705 2.707 2.709 0.004
Cu4 I3 2.679 2.679 2.679 2.68 0.001
Cu1 S1 2.295 2.295 2.295 2.294 -0.001
Cu2 S2 2.284 2.284 2.283 2.282 -0.002
Cu3 S3 2.321 2.319 2.317 2.319 -0.002
Cu1 Cu4 2.629 2.622 2.621 2.625 -0.004
S16
Cu3 I4 2.625 2.622 2.622 2.621 -0.004
Cu4 I2 2.718 2.714 2.715 2.713 -0.005
C23 C24 1.523 1.53 1.519 1.518 -0.005
Cu4 S4 2.29 2.289 2.287 2.283 -0.007
S3 C18 1.839 1.835 1.833 1.831 -0.008
S2 C10 1.811 1.815 1.811 1.802 -0.009
S4 C23 1.808 1.801 1.798 1.797 -0.011
N2 C24 1.477 1.46 1.46 1.464 -0.013
S3 C19 1.829 1.827 1.829 1.814 -0.015
O1 C8 1.234 1.226 1.224 1.218 -0.016
C13 C14 1.55 1.539 1.535 1.533 -0.017
S1 C7 1.83 1.827 1.826 1.809 -0.021
C19 C20 1.514 1.503 1.501 1.491 -0.023
S4 C22 1.813 1.81 1.799 1.788 -0.025
N1 C9 1.471 1.454 1.436 1.446 -0.025
N2 C21 1.464 1.446 1.437 1.433 -0.031
C17 C18 1.51 1.494 1.495 1.475 -0.035
C1 C2 1.551 1.489 1.475 1.509 -0.042
S2 C11 1.811 1.807 1.795 1.763 -0.048
C1 C6 1.523 1.526 1.519 1.471 -0.052
N1 C8 1.365 1.345 1.348 1.313 -0.052
C5 C6 1.508 1.503 1.505 1.455 -0.053
C3 C4 1.497 1.492 1.5 1.427 -0.07
C15 C16 1.481 1.477 1.478 1.398 -0.083
S17
Table S6. Bond distances of 3 at four different temperatures.
Atom1 Atom2 d-123K d-173K d-223K d-298K (d-298K) -
(d-123K)
Cu1 I2 2.632 2.767 2.768 2.765 0.133
Cu3 I3 2.639 2.717 2.724 2.731 0.092
S1 C6 1.846 1.835 1.835 1.904 0.058
Cu1 Cu2 2.765 2.775 2.787 2.815 0.05
Cu1 Cu4 2.703 2.718 2.732 2.747 0.044
Cu2 Cu4 2.771 2.781 2.793 2.814 0.043
Cu2 I3 2.649 2.686 2.689 2.692 0.043
Cu2 Cu3 2.698 2.709 2.723 2.735 0.037
Cu3 Cu4 2.723 2.734 2.747 2.76 0.037
C1 C2 1.529 1.533 1.526 1.562 0.033
C19 C20 1.527 1.538 1.522 1.558 0.031
Cu1 Cu3 2.643 2.65 2.659 2.672 0.029
N1 C9 1.456 1.469 1.465 1.477 0.021
C16 C17 1.526 1.526 1.535 1.546 0.02
C9 C10 1.53 1.516 1.523 1.549 0.019
N2 C24 1.457 1.45 1.457 1.47 0.013
O1 C8 1.227 1.225 1.224 1.238 0.011
Cu4 I4 2.684 2.684 2.688 2.694 0.01
S2 C11 1.811 1.808 1.802 1.82 0.009
C13 C14 1.513 1.512 1.514 1.521 0.008
N2 C21 1.46 1.465 1.466 1.467 0.007
Cu2 I4 2.668 2.67 2.675 2.672 0.004
Cu3 S3 2.297 2.299 2.302 2.301 0.004
Cu1 S1 2.309 2.308 2.31 2.311 0.002
Cu4 I2 2.649 2.653 2.654 2.648 -0.001
Cu4 S4 2.308 2.306 2.309 2.306 -0.002
C5 C6 1.523 1.522 1.53 1.521 -0.002
Cu4 I1 2.667 2.667 2.668 2.663 -0.004
S3 C19 1.82 1.812 1.816 1.816 -0.004
C7 C8 1.518 1.524 1.505 1.514 -0.004
S3 C18 1.829 1.829 1.832 1.824 -0.005
C23 C24 1.516 1.515 1.521 1.51 -0.006
S18
Cu2 S2 2.309 2.308 2.309 2.303 -0.006
S4 C23 1.809 1.808 1.808 1.802 -0.007
C11 C12 1.517 1.519 1.511 1.509 -0.008
C15 C16 1.517 1.517 1.513 1.508 -0.009
Cu3 I4 2.775 2.774 2.773 2.764 -0.011
S1 C7 1.815 1.811 1.811 1.799 -0.016
N1 C8 1.374 1.367 1.369 1.355 -0.019
C3 C4 1.527 1.527 1.516 1.507 -0.02
O2 C20 1.236 1.213 1.208 1.213 -0.023
C21 C22 1.526 1.518 1.51 1.5 -0.026
S2 C10 1.811 1.807 1.807 1.783 -0.028
Cu1 I1 2.767 2.728 2.733 2.736 -0.031
C13 C18 1.522 1.515 1.518 1.491 -0.031
Cu2 I1 2.682 2.648 2.65 2.651 -0.031
C14 C15 1.538 1.526 1.523 1.507 -0.031
C4 C5 1.514 1.518 1.512 1.482 -0.032
N1 C12 1.455 1.462 1.45 1.418 -0.037
C17 C18 1.52 1.523 1.513 1.482 -0.038
N2 C20 1.357 1.352 1.359 1.318 -0.039
S4 C22 1.809 1.802 1.794 1.769 -0.04
C2 C3 1.521 1.506 1.498 1.475 -0.046
C1 C6 1.517 1.514 1.517 1.464 -0.053
Cu3 I2 2.709 2.637 2.638 2.634 -0.075
Cu1 I3 2.726 2.63 2.631 2.624 -0.102
S19
0.0
0.2
0.4
0.6
0.8
1.0
λ / nm
3526 538
400 450 500 550 600
Iem
2
(a)
400 450 500 550 6000.2
0.4
0.6
0.8
1.0
Iem
λ / nm
1 2 3
538 nm
(b) Figure S9. Photoluminescence spectra of before (a) and after (b) heating at 180 °C.
S20
10 20 30 40 50 60
Inte
nsity
(c)
2Theta / degree
10 20 30 40 50 60
(b)
Figure S10. Powder XRD Patterns of 1; frame image (a), measured (b), and calculated (c).
2.6° 37.7°
(a)
S21
10 20 30 40 50 60
In
tens
ity
2Theta / degree
(c)
10 20 30 40 50 60
(b)
Figure S11. Powder XRD Patterns of 2; frame image (a), measured (b), and calculated (c).
2.6° 37.7°
(a)
S22
10 20 30 40 50 60
(c)
Inte
nsity
2Theta / degree
10 20 30 40 50 60
(b)
Figure S12. Powder XRD Patterns of 3’ (a and b) and 3 (c); frame image (a), measured (b), and calculated (c).
2.6° 37.7°
(a)
S23
0 200 400 600 800 1000
10
20
30
40
50
60
70
80
90
100
-60
-50
-40
-30
-20
-10
0
10 Temperature D
ifference [μV / m
g]
Wei
ght [
%]
Temperature [oC]
178
Figure S13. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) traces for 1. (black solid line : TGA, red dash line : DTA)
0 200 400 600 800 1000
10
20
30
40
50
60
70
80
90
100
-40
-30
-20
-10
0
10
Temperature D
ifference [μV / mg]
W
eigh
t [%
]
Temperature [oC]
203
Figure S14. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) traces for 2. (black solid line : TGA, red dash line : DTA)
S24
0 200 400 600 800 1000
10
20
30
40
50
60
70
80
90
100
-50
-40
-30
-20
-10
0
10 Temperature D
ifference [μV / mg]
Wei
ght [
%]
Temperature [oC]
178
Figure S15. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) traces for 3’. (black solid line : TGA, red dash line : DTA)
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