1

Altering the photochromic properties of N-Salicylideneanilines using a co-crystal

engineering approach

Gabriel M. Mercier†, Koen Robeyns

†, Tom Leyssens

†*

1.1 XRPD graphs of ground mixtures (in blue) B-C4, B-C6, B-C13 and B-C15 versus references B (in

red) and co-formers (in green).

XRPD Pattern of B-C4

XRPD Pattern of B-C6

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XRPD Pattern of B-C13

XRPD Pattern of B-C15

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1.2 TGA thermograms of B-C4, B-C6, B-C13 and B-C15.

TGA thermogram of B-C4. 5% mass loss observed at 160 °C, corresponding to the onset of

degradation.

TGA thermogram of B-C6. 5% mass loss observed at 162 °C corresponds to the onset of degradation.

The initial loss in mass is expected to be due to a loss in solvent that was used for the liquid assisted

grinding experiments.

Step -4.9395 %

-0.2746 mg

GM03C4 TGA1, 16.03.2014 09:47:42GM03C4 TGA1, 5.5600 mg

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Step -5.0012 %

-0.2576 mg

GM03C6 TGA1, 16.03.2014 11:13:06GM03C6 TGA1, 5.1500 mg

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GM 03 C6 T GA 1GM 03 C6 T GA 1GM 03 C6 T GA 1GM 03 C6 T GA 1 1 7 .0 3 .2 01 4 1 7 :3 9 :2 71 7 .0 3 .2 01 4 1 7 :3 9 :2 71 7 .0 3 .2 01 4 1 7 :3 9 :2 71 7 .0 3 .2 01 4 1 7 :3 9 :2 7

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TGA thermogram of B-C13. 5% loss observed at 155 °C corresponds to the onset of degradation.

TGA thermogram of B-C15. 5% mass loss observed at 130 °C corresponds to the onset of

degradation.

Step -5.2419 % -0.3208 m g

GM03C15(1/1) T GA1, 22.02.2014 00:31:46GM03C15(1/1) T GA1, 6.1200 m g

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0 2 4 6 8 1 0 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44

SSSS T AT AT AT A RRRR eeee S W 9 .1 0 S W 9 .1 0 S W 9 .1 0 S W 9 .1 0U C L P o l y : G MU C L P o l y : G MU C L P o l y : G MU C L P o l y : G M

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1.3 DSC thermograms of B-C4, B-C6, B-C13 and B-C15.

DSC thermogram of B-C4. Melting point Onset at 82 ± 1 °C and Endset at 85 ± 1 °C. Based on the TGA

data, the second peak with onset at 123 ± 1 °C corresponds to the beginning of mass loss. Melting

point of B alone is 82 - 86 °C and C4 alone is 208 - 211 °C.

DSC thermogram of B-C6. Melting point Onset at 84 ± 1 °C and Endset at 88 ± 1 °C. Melting point of B

alone is 82 - 86 °C and C6 is 220 °C.

Integral -40.40 mW°C

Endset 127.15 °C

Endset 85.27 °C Onset 123.05 °C

Int egral -33.06 mW°C

Onset 82.66 °C

]2[GM03C4 DSC 1GM03C4 DSC 1, 9.9300 mgmW

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Integral -62.94 mW°C

Endset 88.51 °C

Onset 84.01 °C

]2[GM03C6 DSC 2

GM03C6 DSC 2, 10.1000 mgmW

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DSC thermogram of B-C13. Melting point Onset at 103 ± 1 °C and Endset not measured. Pattern at 83

°C correspond to solvent traces evaporation (small mass loss at 83°C according to TGA). Melting point

of B alone is 82 - 86 °C and C13 alone is 135 °C.

DSC thermogram of B-C15. Melting point Onset at 101 ± 1 °C and Endset at 105 ± 1 °C. Pattern at 82

°C correspond to either solvent traces evaporation or small excess of B versus C15 leading to a small

eutectic melt. Melting point of B alone is 82 - 86 °C and C15 alone is 103 °C.

O ns et 83.52 °C

O ns et 102.73 °C

]2[GM03C 13 DSC1GM03C13 DSC1, 8.8600 m g

m W

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^ e x o^ e x o^ e x o^ e x o G M 0 3 C 1 3 d s c 1G M 0 3 C 1 3 d s c 1G M 0 3 C 1 3 d s c 1G M 0 3 C 1 3 d s c 1 1 4 .0 3 .2 0 1 4 1 3 :1 1 : 4 91 4 .0 3 .2 0 1 4 1 3 :1 1 : 4 91 4 .0 3 .2 0 1 4 1 3 :1 1 : 4 91 4 .0 3 .2 0 1 4 1 3 :1 1 : 4 9

SSSS T AT AT AT A RRRR eeee S W 9 .1 0 S W 9 .1 0 S W 9 .1 0 S W 9 .1 0U C L P o l y : G MU C L P o l y : G MU C L P o l y : G MU C L P o l y : G M

Int egra l -72.46 m W°C

Ends e t 105.09 °C

O ns e t 82.06 °C

O ns et 101.2 8 °C

]2[GM03C15 1/1

GM03C15 1/1, 8.6800 m gm W

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1.4 TGA and DSC thermograms of A-C10 co-crystal.

TGA thermogram of A-C10. 5% mass loss observed at 102 ± 2 °C, corresponding to the onset of

degradation.

DSC thermogram of A-C10. Melting point Onset at 80 ± 1 °C. Melting point of A alone is 49 ± 1 °C and

C10 alone is 92 °C.

Step -5.196 4 % -0.287 4 m g

GM04C10 TGA1, 22.02.2014 01:56:55GM04C10 TGA1, 5.5300 m g

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SSSS T AT AT AT A RRRR eeee S W 9 .1 0 S W 9 .1 0 S W 9 .1 0 S W 9 .1 0U C L P o l y : G MU C L P o l y : G MU C L P o l y : G MU C L P o l y : G M

Int egral -798.99 mJ

Onset 80.43 °C

]2[ GM04C10 DSC 3

GM04C 10 DSC 3, 0.0000 mgmW

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^ e x o^ e x o^ e x o^ e x o G M 0 4 C 1 0 D SC 3 2 ? m inG M 0 4 C 1 0 D SC 3 2 ? m inG M 0 4 C 1 0 D SC 3 2 ? m inG M 0 4 C 1 0 D SC 3 2 ? m in 1 7 .1 2 .2 0 1 3 1 0 :3 0 :4 61 7 .1 2 .2 0 1 3 1 0 :3 0 :4 61 7 .1 2 .2 0 1 3 1 0 :3 0 :4 61 7 .1 2 .2 0 1 3 1 0 :3 0 :4 6

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1.5 DRS Spectra of A+C10 (physical mixture) versus references (A and A-C10).

Physical mixture (yellow graph) is close to A graph compared to A-C10 co-crystal. The higher

absorption band around 300 nm is due to C10 absorption. Note the superposition between physical

Mixture and A isn’t perfect probably due to a small amount of co-crystal formed during the mixing

process.