2 Direct Visualization of Crystal Formation and Growth …
49
phase such as mechanofluorochromic molecules. The method represents a direct
visualization of Ostwald’s rule of stages during the phase change of organic molecular
solids, including the inhomogeneous phenomena.
Acknowledgements The authors thank Mr. Jun-ichi Fujimori, Ms. Yukino Suzuki, Ms. Mai
Saigusa, and Prof. Naoki Kanayama (Shinshu University); Dr. Mitsuo Hara and Prof. Takahiro
Seki (Nagoya University); and Dr. Ryohei Yasukuni, and Prof. Marc Lamy de la Chapelle (Paris 13
University) for their support for the experiment and kind discussion. We also thank Dr. Kennosuke Itoh (Shinshu University) for the NMR measurements. This work was partly supported
by the Nanotechnology Platform Program, by JSPS KAKENHI Grants Numbers JP21750021,
JP15H01081, JP17H05253, JP19H02686, by the Iketani Science and Technology Foundation, and
by the JGC-S Scholarship Foundation.
References
1. Wolde, P.R., Frenkel, D.: Enhancement of protein crystal nucleation by critical density
fluctuations. Science 277, 1975–1978 (1997)
2. Erdemir, D., Lee, A.Y., Myerson, A.S.: Nucleation of crystals from solution: classical and
two-step models. Acc. Chem. Res. 42, 621–629 (2009)
3. Vekilov, P.G.: The two-step mechanism of nucleation of crystals in solution. Nanoscale 2,
2346–2357 (2010a)
4. Schwoerer, M., Wolf, H.C.: Organic Molecular Solids. Wiley-VCH, Weinheim, Germany
(2007)
5. Ye, X., Liu, Y., Lv, Y., Liu, G., Zheng, X., Han, Q., Jackson, K.A., Tao, X.: In situ microscopic observation of the crystallization process of molecular microparticles by fluorescence
switching. Angew. Chem. Int. Ed. 54, 7976–7980 (2015)
6. Tran, V.L., Genot, V., Audibert, J.F., Prokazov, Y., Turbin, E., Zuschratter, W., Kim, H.J.,
Jung, J., Park, S.Y., Pansu, R.B.: Nucleation and growth during a fluorogenic precipitation in a
micro-flow mapped by fluorescence lifetime microscopy. New J. Chem. 40, 4601–4605 (2016)
7. Zheng, C., Zang, Q., Nie, H., Huang, W., Zhao, Z., Qin, A., Hu, R., Tang, B.Z.: Fluorescence
visualization of crystal formation and transformation processes of organic luminogens with
crystallization-induced emission characteristics. Mater. Chem. Front. 2, 180–188 (2018)
8. Halik, M., Wenseleers, W., Grasso, C., Stellacci, F., Zojer, E., Barlow, S., Bredas, J.L., Perry,
J.W., Marder, S.R.: Bis(dioxaborine) compounds with large two-photon cross sections, and
their use in the photodeposition of silver. Chem. Commun. 1490–1491 (2003)
9. Cogne-Laage, E., Allemand, J.F., Ruel, O., Baudin, J.B., Croquette, V., Blanchard-Desce, M.,
Jullien, L.: Diaroyl(methanato)boron difluoride compounds as medium-sensitive two-photon
fluorescent probes. Chem. Eur. J. 10, 1445–1455 (2004)
10. Ono, K., Yoshikawa, K., Tsuji, Y., Yamaguchi, H., Uozumi, R., Tomura, M., Taga, K., Saito,
K.: Synthesis and photoluminescence properties of BF2 complexes with 1,3-diketone ligands.
Tetrahedron 63, 9354–9358 (2007)
11. Zhang, G.Q., Lu, J.W., Sabat, M., Fraser, C.L.: Polymorphism and reversible mechanochromic
luminescence for solid-state difluoroboron avobenzone. J. Am. Chem. Soc. 132, 2160–2162
(2010)
12. Zhang, G.Q., Singer, J.P., Kooi, S.E., Evans, R.E., Thomas, E.L., Fraser, C.L.: Reversible solidstate mechanochromic fluorescence from a boron lipid dye. J. Mater. Chem. 21, 8295–8299
(2011)
13. Samonina-Kosicka, J., DeRosa, C.A., Morris, W.A., Fan, Z.Y., Fraser, C.L.: Dual-emissive
difluoroboron naphthyl-phenyl beta-diketonate polylactide materials: effects of heavy atom
placement and polymer molecular weight. Macromolecules 47, 3736–3746 (2014)
49
phase such as mechanofluorochromic molecules. The method represents a direct
visualization of Ostwald’s rule of stages during the phase change of organic molecular
solids, including the inhomogeneous phenomena.
Acknowledgements The authors thank Mr. Jun-ichi Fujimori, Ms. Yukino Suzuki, Ms. Mai
Saigusa, and Prof. Naoki Kanayama (Shinshu University); Dr. Mitsuo Hara and Prof. Takahiro
Seki (Nagoya University); and Dr. Ryohei Yasukuni, and Prof. Marc Lamy de la Chapelle (Paris 13
University) for their support for the experiment and kind discussion. We also thank Dr. Kennosuke Itoh (Shinshu University) for the NMR measurements. This work was partly supported
by the Nanotechnology Platform Program, by JSPS KAKENHI Grants Numbers JP21750021,
JP15H01081, JP17H05253, JP19H02686, by the Iketani Science and Technology Foundation, and
by the JGC-S Scholarship Foundation.
References
1. Wolde, P.R., Frenkel, D.: Enhancement of protein crystal nucleation by critical density
fluctuations. Science 277, 1975–1978 (1997)
2. Erdemir, D., Lee, A.Y., Myerson, A.S.: Nucleation of crystals from solution: classical and
two-step models. Acc. Chem. Res. 42, 621–629 (2009)
3. Vekilov, P.G.: The two-step mechanism of nucleation of crystals in solution. Nanoscale 2,
2346–2357 (2010a)
4. Schwoerer, M., Wolf, H.C.: Organic Molecular Solids. Wiley-VCH, Weinheim, Germany
(2007)
5. Ye, X., Liu, Y., Lv, Y., Liu, G., Zheng, X., Han, Q., Jackson, K.A., Tao, X.: In situ microscopic observation of the crystallization process of molecular microparticles by fluorescence
switching. Angew. Chem. Int. Ed. 54, 7976–7980 (2015)
6. Tran, V.L., Genot, V., Audibert, J.F., Prokazov, Y., Turbin, E., Zuschratter, W., Kim, H.J.,
Jung, J., Park, S.Y., Pansu, R.B.: Nucleation and growth during a fluorogenic precipitation in a
micro-flow mapped by fluorescence lifetime microscopy. New J. Chem. 40, 4601–4605 (2016)
7. Zheng, C., Zang, Q., Nie, H., Huang, W., Zhao, Z., Qin, A., Hu, R., Tang, B.Z.: Fluorescence
visualization of crystal formation and transformation processes of organic luminogens with
crystallization-induced emission characteristics. Mater. Chem. Front. 2, 180–188 (2018)
8. Halik, M., Wenseleers, W., Grasso, C., Stellacci, F., Zojer, E., Barlow, S., Bredas, J.L., Perry,
J.W., Marder, S.R.: Bis(dioxaborine) compounds with large two-photon cross sections, and
their use in the photodeposition of silver. Chem. Commun. 1490–1491 (2003)
9. Cogne-Laage, E., Allemand, J.F., Ruel, O., Baudin, J.B., Croquette, V., Blanchard-Desce, M.,
Jullien, L.: Diaroyl(methanato)boron difluoride compounds as medium-sensitive two-photon
fluorescent probes. Chem. Eur. J. 10, 1445–1455 (2004)
10. Ono, K., Yoshikawa, K., Tsuji, Y., Yamaguchi, H., Uozumi, R., Tomura, M., Taga, K., Saito,
K.: Synthesis and photoluminescence properties of BF2 complexes with 1,3-diketone ligands.
Tetrahedron 63, 9354–9358 (2007)
11. Zhang, G.Q., Lu, J.W., Sabat, M., Fraser, C.L.: Polymorphism and reversible mechanochromic
luminescence for solid-state difluoroboron avobenzone. J. Am. Chem. Soc. 132, 2160–2162
(2010)
12. Zhang, G.Q., Singer, J.P., Kooi, S.E., Evans, R.E., Thomas, E.L., Fraser, C.L.: Reversible solidstate mechanochromic fluorescence from a boron lipid dye. J. Mater. Chem. 21, 8295–8299
(2011)
13. Samonina-Kosicka, J., DeRosa, C.A., Morris, W.A., Fan, Z.Y., Fraser, C.L.: Dual-emissive
difluoroboron naphthyl-phenyl beta-diketonate polylactide materials: effects of heavy atom
placement and polymer molecular weight. Macromolecules 47, 3736–3746 (2014)