Conformational polymorphs and solid-state polymerization of 9-(1,3-butadiynyl)carbazole derivatives

Abstract

The novel diacetylenes, 9-(5-(4-nitrophenoxy)penta-1,3-diyn-1-yl)-9H-carbazole (1) and 4-((5-(9H-carbazol-9-yl)penta-2,4-diyn-1-yl)oxy)benzonitrile (2), were prepared and characterized by crystallographic analyses. Compound 1 gave two conformational polymorphs, 1-(I) and 1-(II), whose differences were concluded to originate in intermolecular interactions among nitrophenyl groups. Crystal 1-(I) and 2 had suitable molecular arrangements for solid-state polymerization and polymerized by thermal annealing to give crystalline polydiacetylenes (PDAs). While an arrangement of 1-(II) was unsuitable for the polymerization. The PDAs showed broad absorption from UV to

Crystal polymorphs of 6-[(phenylcarbamoyl)oxy]hexa-2,4-diyn-1-yl isonicotinate

“…In another example, reported by Hocek et al (2002), one polymorphic form is supposed to have a suitable molecular arrangement for solid-state polymerization, but the solid-state reactivity was not discussed. Boughman's work (Wilson et al, 1982), recent work from Lauher's group (Hsu et al, 2012) and our work (Tabata et al, 2016) all report active and inactive polymorphs. Therefore, this work is the fifth report which treats the difference in solid-state polymerization reactivity of diacetylenes under ambient pressure between polymorphs.…”

“…One polymorph was inert for thermal polymerization, but the other showed polymerization reactivity by thermal annealing or photoirradiation. To the best of our knowledge, this study is the fifth report looking at the difference in solid-state polymerization reactivity of polymorphic diacetylenes under ambient pressure (Hanson, 1975;Hocek et al, 2002;Wilson et al, 1982;Hsu et al, 2012;Tabata et al, 2016).…”

Preparation and Utility of N-Alkynyl Azoles in Synthesis

“…Terminal alkynes, including N -alkynyl amides, participate in nucleophilic addition and coupling reactions [59], and similar reactions have also been reported for N -alkynyl azoles. In 1992, Paley published one of the first reactions of an N -alkynyl azole (Scheme 32, Reaction (1) [14]).…”

5-[Phenyl(pyridin-4-yl)amino]penta-2,4-diyn-1-ol

“…However, except for the case of iodine or nitrogen, these attempts have resulted in failure owing to limitations on molecular arrangement for solidstate polymerization of diacetylenes (Baughman, 1974), where the molecular arrangement is expressed in terms of stacking intervals and the inclination angle of the diacetylene unit to the stacking axis. Some heteroatom-substituted polydiacetylenes have been developed successfully (Galli et al, 1988(Galli et al, , 1989Sarkar et al, 1998;Okuno et al, 2006;Tabata et al, 2012Tabata et al, , 2016Tokutome et al, 2012).…”