Pressure-Induced Polymerization of Diiodobutadiyne in Assembled Cocrystals.
Diiodobutadiyne forms cocrystals with bis(pyridyl)oxalamides in which the diyne alignment is near the ideal parameters for topochemical polymerization to the ordered conjugated polymer, poly-(diiododiacetylene) (PIDA). Nonetheless, previous efforts to induce polymerization in these samples via heat...
| Publicado en: | Journal of the American Chemical Society Vol. 130; no. 13; pp. 4415 - 4421 |
|---|---|
| Autores principales: | , , , , , , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
4/2/2008
|
| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=31648178&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 31648178 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 4/2/2008 vid: 130 iid: 13 pid: 997 pub: American Chemical Society artinfo: ui: 31648178 10.1021/ja0782910 ppf: 4415 ppct: 6 formats: tig: atl: Pressure-Induced Polymerization of Diiodobutadiyne in Assembled Cocrystals. aug: au: Wilhelm, Christopher Boyd, Stephen A. Chawda, Samrat Fowler, Frank W. Goroff, Nancy S. Halada, Gary P. Grey, Clare P. Lauher, Joseph W. Liang Luo Martin, C. David Parise, John B. Tarabrella, Cathy Webb, Jeffrey A. affil: Department of Chemistry, State University of New York, Stony Brook, New York 11794-3400 Department of Geosciences, State University of New York, Stony Brook, New York 11794-2100 Department of Materials Science and Engineering, State University of New York, Stony Brook, New York 11794-2275 su: Polymerization Crystals Polymers Optical diffraction Chemical reactions sug: subj: Polymerization Crystals Polymers Optical diffraction Chemical reactions ab: Diiodobutadiyne forms cocrystals with bis(pyridyl)oxalamides in which the diyne alignment is near the ideal parameters for topochemical polymerization to the ordered conjugated polymer, poly-(diiododiacetylene) (PIDA). Nonetheless, previous efforts to induce polymerization in these samples via heat or irradiation were unsuccessful. We report here the successful ordered polymerization of diiodobutadiyne in these cocrystals, by subjecting them to high external pressure (0.3-10 GPa). At the lower end of the pressure range, the samples contain primarily monomer, as demonstrated by X-ray diffraction studies, but some polymerization does occur, leading to a pronounced color change from colorless to blue and to the development of intense Raman peaks at 962, 1394, and 2055 cm, corresponding to the poly-(diacetylene). At higher pressures, the samples turn black and contain primarily polymer, as determined by solid-state NMR and Raman spectroscopy. Both density functional theory calculations (B3LYP/LanL2DZ) and comparisons to authentic samples of PIDA have confirmed the data analysis. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2008 holdings: @attributes: islocal: N |
|---|