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Single-component optically transparent film of a star-shaped cage silsesquioxane derivative and its phase change behavior

Abstract

Modularly synthesized giant molecular clusters containing rigid spherical molecules as element-blocks are a new class of unconventional macromolecules. Among various candidates for rigid spherical molecules, cage octasilsesquioxane (T8) frameworks have been demonstrated to be an efficient building block for designing well-defined 3D solid materials due to the flexible designability of their organic substituents. Here, we studied the crystalline phase and phase transition behavior of an optically transparent film of star-shaped (heptaisobutyl-T8-silsesquioxy)propyl-substituted octadimethylsiloxy-Q8-silsesquioxane (star-POSS) by DSC and wide-angle X-ray scattering (WAXS) measurements. This star-POSS exhibited a crystalline phase with a hexagonal system at room temperature and underwent melting above the melting temperature (Tm). Furthermore, the specimens underwent recrystallization even at temperature above Tm, resulting in the same hexagonal system with slightly larger a- and c-axis lengths. The amorphous state of the surrounding isobutyl substituents on the T8-cage framework provides an optically transparent film of star-POSS.

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Acknowledgements

This work was supported by a Grant-in-Aid for Scientific Research (No. 19H02764) from the Ministry of Education, Culture, Sports, Science, and Technology, Government of Japan. We thank Prof. Tsuyoshi Kawai, Ms. Yoshiko Nishikawa, and Mieko Yamagaki of Nara Institute of Science and Technology for performing MALDI-TOF-MS supported by the Nanotechnology Platform. The WAXS measurements were performed at BL-10C in Photon Factory, KEK, Japan (under Approval No. 2021G569).

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Correspondence to Shinichi Sakurai or Kensuke Naka.

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Suzuki, R., Li, L., Imoto, H. et al. Single-component optically transparent film of a star-shaped cage silsesquioxane derivative and its phase change behavior. Polym J 54, 1179–1190 (2022). https://doi.org/10.1038/s41428-022-00674-4

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