Solid-State Polymerization Behavior of 1,3-Bis(3-quinolyl)-1,4-butadiyne |
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Authors: | Tiesheng Li Shuji Okada Hirohito Umezawa Hitoshi Kasai Hachiro Nakanishi Satya S Talwar Tatsumi Kimura Hiro Matsuda |
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Affiliation: | (1) Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Sendai 980-8577, Japan;(2) Department of Chemistry, Indian Institute of Technology, Bombay, Powai, Mumbai, 400 076, India;(3) Photonics Research Institute, National Institute of Advanced Industrial Science and Technology, 1-1-1 Higashi, Tsukuba 305-8565, Japan;(4) Department of Chemistry, Zhengzhou University, Daxue road 75, Zhengzhou, 450052, China;(5) Department of Polymer Science and Engineering, Faculty of Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa 992-8510, Japan;(6) Department of Chemistry and Biochemistry, Fukushima National College of Technology, 30 Nagao, Taira Kamiarakawa, Iwaki 970-8034, Japan;(7) Emeritus Scientist, Department of Physics, Indian Institute of Technology, Bombay, Powai, Mumbai, 400 076, India |
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Abstract: | Summary 1,4-Bis(3-quinolyl)-1,3-butadiyne (DQ) is known to be polymerized in solid state to give the corresponding polydiacetylene.
However, the polymer yield of DQ bulk crystals is low. Thus, we prepared several types of DQ crystals by different procedures
to find the reason for the low polymer yield. We found three modifications of DQ crystals and they were evaluated by spectroscopic
measurements and X-ray diffraction. DQ bulk crystals (Crystal I) and thermally grown DQ crystals on Crystal I (Crystal II)
have the same structure classified to Type A, which gives regular polydiacetylene structure in low polymer yields. DQ crystals
grown on glass plates by sublimation (Crystal III) belong to the second modification of Type B. DQ nanocrystals prepared by
the reprecipitation method (Crystal IV) are Type B, and thermally grown DQ crystals on nanocrystals (Crystal V) are Type C.
Crystals of Types B and C could be polymerized in low yields without showing excitonic absorption of polydiacetylene indicating
irregular polymerization other than 1,4-addition. For crystals of Type A, we found that the 1,4-addition polymerization proceeded
only in near-surface portions of the crystals. It can be plausibly explained that mobile monomers in the near-surface portion
are only able to take part in their polymerization, resulting in low polymer conversion. |
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