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Most investigations on soluble poly(diacetylene)s to date have been carried out with dodeca-5,7-diyne bis(toluenesulfonate) (PTS-12), dodeca-5,7-diyne bis(butylcarboxymethyl carbamate) (P4BCMU), or closely related monomers; for the original investigations, see: Wenz, G.; Müller, M. A.; Schmidt, M.; Wegner, G. Macromolecules 1984, 17, 837.
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See Supporting Information for additional figures and detailed discussion
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See Supporting Information for additional figures and detailed discussion.
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50249137790
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It should be acknowledged that the hexyl-substituted 2b constituted a notable exception; see Supporting Information
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The other monomers (1a-c as well as 2a and 2b) were not polymerizable, in agreement with the geometric features inappropriate for a topochemical polymerization. In the case of 1b·3, UV irradiation caused a significant color change to bright orange. However, acetone extraction of the sample after 3 h of irradiation only yielded 3% of insoluble material; longer irradiation generated more material, but only in total isolated yields of below 5, Nevertheless, the 1H NMR and Raman spectra of the obtained material were consistent with poly(diacetylene) formation and resembled those of polymer P2c. As the crystal structure of 1b·3 was found to be similar to those of 1a·3 and 2c and, in particular, the geometric parameters of the diacetylene packing were almost identical, the surprising lack of bulk polymerizability may tentatively be attributed to the overall poor crystal quality
-
1H NMR and Raman spectra of the obtained material were consistent with poly(diacetylene) formation and resembled those of polymer P2c. As the crystal structure of 1b·3 was found to be similar to those of 1a·3 and 2c and, in particular, the geometric parameters of the diacetylene packing were almost identical, the surprising lack of bulk polymerizability may tentatively be attributed to the overall poor crystal quality.
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