# Fileset

[SI.pdf](https://mdr.nims.go.jp/filesets/03426cb9-51b5-4ec6-a614-0efb4e2e9f7e/download)

## Creator

[Yuichi Hirai](https://orcid.org/0000-0002-0252-1243), Anna Wrona-Piotrowicz, Janusz Zakrzewski, Magdalena Ciechańska, [Takahito Ohmura](https://orcid.org/0000-0001-7528-566X), [Takashi Takeda](https://orcid.org/0000-0003-2510-4562), [Takayuki Nakanishi](https://orcid.org/0000-0003-3412-2842), Rémi Métivier, Clémence Allain

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## Other metadata

[Mechanofluorochromism and self-recovery of alkylsilylpyrene-1-carboxamides](https://mdr.nims.go.jp/datasets/8777b80a-2e1c-43e3-b7e2-f65d2f3989e6)

## Fulltext

Justification for an urgent publication in Chemical CommunicationsSupplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 20011Supporting InformationManuscript: “Mechanofluorochromism and Self-Recovery of Alkylsilylpyrene-1-Carboxamides” Authors: Yuichi Hirai,*a Anna Wrona-Piotrowicz,b Janusz Zakrzewski,b Magdalena Ciechanska,b Takahito Ohmura,d Takashi Takeda,a Takayuki Nakanishi,a Rémi Métivier*c and Clémence Allain*cElectronic Supplementary Material (ESI) for Journal of Materials Chemistry C.This journal is © The Royal Society of Chemistry 2023Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 20012Apparatus1H and 13C NMR spectra were recorded in CDCl3 on a Bruker ARX 600 MHz (600 MHz for 1H and 151 MHz for 13C). Spectra were recorded at room temperature (291 K), chemical shifts are in ppm and coupling constants in Hz.Me3: 1H NMR (CDCl3): δ 8.35 (s, 1H), 8.25 (d, J = 9.0, 1H), 8.18 (pseudo-t, J = 6.6, 2H), 8.10 (d, J = 9.6, 1H), 8.08 (d, J = 9.0, 1H), 8.05 (d, J = 9.0, 1H), 8.02 (t, J = 7.8, 1H), 5.74 (s, 1H), 1.64 (s, 9H), 0.55 (s, 9H); 13C NMR (CDCl3): δ 170.56, 138.94, 134.29, 131.45, 131.14, 130.82, 130.47, 128.23, 127.91, 127.44, 127.38, 126.37, 125.44, 125.18, 124.81, 124.38, 124.12, 52.63, 29.06, 0.54.Me2Et: 1H NMR (CDCl3): δ 8.33 (s, 1H), 8.25 (d, J = 9.1, 1H), 8.18 (pseudo-t, J = 7.2, 2H), 8.08 (d, J = 9.6, 1H), 8.05 (d, J = 9.0, 1H), 8.02 (d, J = 7.8, 1H), 8.02 (t, J = 7.8, 1H), 5.70 (s, 1H), 1.63 (s, 9H), 1.01–1.06 (m, 5H), 0.53 (s, 6H); 13C NMR (CDCl3): δ 170.56, 139.16, 133.33, 131.51, 131.47, 130.85, 130.42, 128.21, 127.90, 127.49, 127.41, 126.38, 125.44, 125.18, 124.83, 124.41, 124.15, 52.65, 29.06, 8.24, 7.67, –1.83.Et3: 1H NMR (CDCl3): δ 8.32 (s, 1H), 8.25 (d, J = 9.0, 1H), 8.18 (t, J = 6.6, 2H), 8.10 (d, J = 9.6, 2H), 8.05 (d, J = 9.0, 1H), 8.01 (d, J = 7.2, 1H), 5.66 (s, 1H), 1.64 (s, 9H), 1.14–1.10 (m, 6H), 1.05–1.02 (m, 9H); 13C NMR (CDCl3): δ 170.57, 139.48, 132.22, 131.46, 131.29, 130.84, 130.28, 128.13, 127.85, 127.55, 127.45, 126.36, 125.78, 125.43, 125.16, 124.81, 124.40, 124.19, 52.66, 28.96, 7.70, 4.05.Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 20013Figure S1. A sample preparation procedure for MFC spectroscopy (at 23˚C, 43%RH). White dotted circles show the sample positions under a room light.Figure S2. Normalised emission spectra of Me3, Me2Et, and Et3 at room temperature (RT) after grinding (blue: 0 min (ground), purple, pink, and red: 10, 20, and 30 min at RT after grinding, respectively, λex = 340 nm, in the solid state).Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 20014Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 20015Figure S3. DSC thermograms of Me3, Me2Et, and Et3.Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 20016Figure S4. Simulated and experimental (pristine and ground) PXRD patterns and photos under room light and UV irradiation of Me3, Me2Et, and Et3.Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 20017Figure S5. a) ORTEP view (top, thermal ellipsoids are shown at 50% probability and hydrogen atoms are omitted for clarity) and packing diagram of two neighboring molecules (bottom) and b) Hirshfeld surfaces with fingerprint plots for specific pairs of atom-Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 20018types of Me3, Me2Et, and Et3 (grey shadow: outline of the complete fingerprint plot, di and de: distances from the Hirshfeld surfaces to the nearest nucleus inside and outside the surface, respectively).Figure S6. Schematic of nanomechanical tests.Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 20019Figure S7. Emission intensity ratios between VIS (λem ~ 410–419 nm) and UV (λem ~ 388 nm) bands in Et3 upon cooling and heating processes (plots were overlapped).Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 200110Table S1. Summary of selected crystallographic parameters of Me3 in temperature-variable SCXRD experiments.T / K 123 K 153 K 183 K 213 K 243 K 273 K 303 K 333 K 363 K 393 KDcalc./ g cm-3 1.197 1.185 1.181 1.169 1.162 1.153 1.146 1.134 1.126 1.119 µ/mm-1 0.126 0.125 0.125 0.123 0.123 0.122 0.121 0.120 0.119 0.118 a/Å 10.9996 11.0400 11.0479 11.0892 11.1134 11.1497 11.1876 11.2381 11.2812 11.3306b/Å 9.9013 9.8882 9.8798 9.8918 9.8968 9.9080 9.9160 9.9380 9.9489 9.9451c/Å 19.2782 19.4597 19.5539 19.6740 19.7565 19.8583 19.9362 20.0348 20.1153 20.1886α/° 90 90 90 90 90 90 90 90 90 90 β/° 99.065 99.626 100.010 100.410 100.743 101.193 101.696 102.077 102.514 102.876γ/° 90 90 90 90 90 90 90 90 90 90 V/Å3 2073.38 2094.43 2101.84 2122.55 2134.87 2152.03 2165.72 2188.04 2204.01 2217.69Z 4 4 4 4 4 4 4 4 4 4 Z’ 1 1 1 1 1 1 1 1 1 1 Qmin/° 2.140 2.317 2.317 2.312 2.098 2.306 2.304 2.298 2.295 2.295 Qmax/° 26.372 26.363 26.371 26.370 26.369 26.372 26.367 26.373 26.372 26.371 Measured Refl. 49858 50991 48366 54038 51892 48310 51373 48414 48512 50075 Independent Refl. 4248 4292 4312 4349 4373 4404 4433 4473 4502 4528 Refl. with I > 2(I) 3755 3525 3353 3182 3186 2944 3079 2653 2782 2560 Rint 0.0401 0.0338 0.0383 0.0308 0.0269 0.0382 0.0263 0.0397 0.0502 0.0597 GooF 1.067 1.064 1.061 1.065 1.072 1.086 1.688 1.074 1.077 1.235 wR2 (all data) 0.1157 0.1479 0.1769 0.1952 0.2306 0.2519 0.2374 0.2429 0.2857 0.3475 wR2 0.1121 0.1391 0.1651 0.1786 0.2063 0.2219 0.2224 0.2148 0.2503 0.3010 Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 200111R1 (all data) 0.0429 0.0600 0.0720 0.0791 0.0862 0.1000 0.0817 0.0943 0.0981 0.1162 R1 0.0386 0.0505 0.0592 0.0620 0.0660 0.0725 0.0619 0.0589 0.0698 0.0851 *Formula: C24H27NOSi, Formula weight: 373.55, Color: clear colorless, Shape: needle, Size: 0.81 × 0.11× 0.08 mm3, Crystal system: monoclinic, Space group: P21/c, Wavelength: 0.71073 Å, Radiation type: Mo Kα for all measurementsTable S2. Summary of selected crystallographic parameters of Me2Et in temperature-variable SCXRD experiments.T / K 123 K 153 K 183 K 213 K 243 K 273 K 303 K 333 K 363 K 393 KDcalc./ g cm-3 1.199 1.194 1.189 1.184 1.178 1.171 1.166 1.156 1.147 1.138 µ/mm-1 0.124 0.124 0.123 0.123 0.122 0.121 0.121 0.120 0.119 0.118 a/Å 10.7771 10.8011 10.8255 10.8510 10.8797 10.9116 10.9394 10.9844 11.0196 11.0625b/Å 9.85420 9.86550 9.8799 9.8897 9.9095 9.9285 9.9405 9.9710 9.9958 10.0230c/Å 20.7765 20.7927 20.8127 20.8306 20.8527 20.8812 20.8935 20.9290 20.9717 21.0259α/° 90 90 90 90 90 90 90 90 90 90 β/° 103.243 103.322 103.394 103.454 103.511 103.567 103.629 103.709 103.749 103.939γ/° 90 90 90 90 90 90 90 90 90 90 V/Å3 2147.78 2156.02 2165.48 2174.06 2185.97 2199.07 2208.06 2226.97 2243.82 2262.69Z 4 4 4 4 4 4 4 4 4 4 Z’ 1 1 1 1 1 1 1 1 1 1 Qmin/° 2.299 2.297 2.294 2.292 2.009 2.284 2.281 2.003 2.270 2.264 Qmax/° 26.371 26.370 26.370 26.371 26.372 26.372 26.371 26.371 26.372 26.371 Measured Refl. 52547 55187 50407 53370 55529 55631 53774 56494 54290 59552 Independent Refl. 4392 4408 4433 4449 4472 4506 4525 4568 4603 4638 Refl. with I > 2(I) 4015 4022 3973 3946 3903 3904 3828 3791 3675 3549 Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 200112Rint 0.0326 0.0333 0.0303 0.0311 0.0282 0.0270 0.0362 0.0272 0.0310 0.0252 GooF 1.122 1.060 1.065 1.074 1.064 1.077 1.081 1.105 1.080 1.091 wR2 (all data) 0.1200 0.1126 0.1164 0.1208 0.1254 0.1354 0.1504 0.1632 0.1944 0.2206 wR2 0.1126 0.1099 0.1124 0.1168 0.1204 0.1305 0.1435 0.1546 0.1801 0.2043 R1 (all data) 0.0455 0.0411 0.0430 0.0444 0.0455 0.0488 0.0536 0.0571 0.0688 0.0741 R1 0.0407 0.0384 0.0390 0.0402 0.0409 0.0439 0.0471 0.0495 0.0549 0.0633 *Formula: C25H29NOSi, Formula weight: 387.58, Color: clear colorless, Shape: block, Size: 0.64 × 0.22× 0.17 mm3, Crystal system: monoclinic, Space group: P21/c, Wavelength: 0.71073 Å, Radiation type: Mo Kα for all measurementsTable S3. Summary of selected crystallographic parameters of Et3 in temperature-variable SCXRD experiments.T / K 123 K 153 K 183 K 213 K 243 K 273 K 303 K 333 K 363 K 393 KDcalc./ g cm-3 1.193 1.186 1.179 1.173 1.166 1.159 1.150 1.144 1.135 1.124 µ/mm-1 0.120 0.119 0.118 0.118 0.117 0.116 0.116 0.115 0.114 0.113 a/Å 11.8370 11.8802 11.9292 11.9667 12.0081 12.0430 12.0890 12.1154 12.1424 12.1689b/Å 10.4643 10.4692 10.4691 10.4761 10.4878 10.5024 10.5330 10.5447 10.5631 10.5841c/Å 25.3373 25.3536 25.3570 25.3546 25.3608 25.3746 25.3765 25.3643 25.3408 25.2785α/° 90 90 90 90 90 90 90 90 90 90 β/° 132.506 132.411 132.332 132.251 132.157 132.090 132.040 131.856 131.547 131.031γ/° 90 90 90 90 90 90 90 90 90 90 V/Å3 2313.70 2328.3 2341.1 2352.8 2367.7 2381.7 2399.8 2413.5 2432.5 2456.1Z 4 4 4 4 4 4 4 4 4 4 Z’ 1 1 1 1 1 1 1 1 1 1 Qmin/° 2.181 2.176 2.228 2.170 2.224 2.220 2.161 2.212 2.207 2.136 Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 200113Qmax/° 26.371 26.370 26.372 26.371 26.370 26.371 26.370 26.370 26.371 26.372 Measured Refl. 53032 56456 56871 58560 54155 57295 57587 51420 54877 56273 Independent Refl. 4722 4755 4778 4804 4834 4870 4901 4933 4977 5023 Refl. with I > 2(I) 4372 4366 4331 4311 4259 4240 4196 4097 3876 3568 Rint 0.0315 0.0320 0.0324 0.0320 0.0335 0.0303 0.0285 0.0609 0.0272 0.0265 GooF 1.081 1.085 1.073 1.084 1.069 1.089 1.102 1.142 1.076 1.217 wR2 (all data) 0.1147 0.1155 0.1188 0.1257 0.1291 0.1328 0.1476 0.1837 0.2092 0.3004 wR2 0.1126 0.1132 0.1160 0.1222 0.1249 0.1291 0.1426 0.1773 0.1968 0.2765 R1 (all data) 0.0415 0.0418 0.0424 0.0452 0.0464 0.0486 0.0540 0.0596 0.0731 0.0999 R1 0.0390 0.0393 0.0394 0.0417 0.0420 0.0439 0.0478 0.0539 0.0628 0.0853 *Formula: C27H33NOSi, Formula weight: 415.63, Color: clear light brown, Shape: block, Size: 0.51 × 0.41× 0.26 mm3, Crystal system: monoclinic, Space group: P21/c, Wavelength: 0.71073 Å, Radiation type: Mo Kα for all measurementsSupplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 200114Figure S8. Selected intramolecular torsion angles of Me3, Me2Et, and Et3 at 123 K and 393 K (methyl and ethyl groups and hydrogen atoms were omitted for clarity).Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 200115Figure S9. CE-B3LYP energy frameworks of Me3, Me2Et, and Et3 from different perspectives representing the net interaction energy (cut-off: 20.0 kJ mol−1) at 393 K. The blue cylinders are connecting ceters of mass of adjacent molecules, and the diameter of cylinders are proportional to the magnitutde of energy. Opaque red and green shadows highlight the interactions between parallel half-stacked pairs and non-parallel head-to-head pairs without NH⋯O=C hydrogen bonding.