title: Synthesis of the Stable Ordered Conjugated Polymer Poly(dibromodiacetylene) from an Explosive Monomer.
abstract: Dibromobutadiyne is an extremely unstable compound that explodes at room temperature, even under inert atmosphere. This instability has limited the studies of dibromobutadiyne almost entirely to spectroscopic characterization. Here we report an approach to control the reactivity of dibromobutadiyne, via topochemical reaction in cocrystals, leading to the ordered polymer poly(dibromodiacetylene), PBDA. At low temperatures (-15 to -18 °C), dibromobutadiyne can form cocrystals with oxalamide host molecules containing either pyridyl or nitrile side groups, in which halogen bonds align the dibromobutadiyne monomers for topochemical polymerization. The cocrystals with the bis(nitrile) oxalamide host undergo complete ordered polymerization to PBDA, demonstrated by solid-state MAS-NMR, Raman, and optical absorption spectroscopy. Once formed, the polymer can be separated from the host; unlike the monomer, PBDA is stable at room temperature.
authors.affiliation: Department of Chemistry, Stony Brook University, Stony Brook, NY 11794-3400 (USA).
authors.forename: Hongjian
authors.initials: H
authors.lastname: Jin
authors.affiliation: Department of Materials Science and Engineering, Stony Brook University, Stony Brook, NY 11794-2275 (USA).
authors.forename: Christopher N
authors.initials: CN
authors.lastname: Young
authors.affiliation: Department of Materials Science and Engineering, Stony Brook University, Stony Brook, NY 11794-2275 (USA).
authors.forename: Gary P
authors.initials: GP
authors.lastname: Halada
authors.affiliation: Department of Geosciences, Stony Brook University, Stony Brook, NY 11794-2100 (USA).
authors.forename: Brian L
authors.initials: BL
authors.lastname: Phillips
authors.affiliation: Department of Chemistry, Stony Brook University, Stony Brook, NY 11794-3400 (USA). Nancy.Goroff@stonybrook.edu.
authors.forename: Nancy S
authors.initials: NS
authors.lastname: Goroff
keywords: conjugated polymers; halogens; low-temperature reaction; polydiacetylene; polymerization