Self-Association and Nitroaromatic-Induced Deaggregation of Pyrene Substituted Pyridine Amides.
The self-assembly features of the bis-pyrene methyl amide functionalized pyridine and benzene "tweezers" 1 and 2 were studied in organic solution and in the solid state. These systems were found to display remarkably different selfassociation features and optical properties, which was rationalized b...
| Publicado en: | Journal of the American Chemical Society Vol. 136; no. 1; pp. 495 - 506 |
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| Autores principales: | , , , , , , , |
| Formato: | Artículo |
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American Chemical Society
1/8/2014
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| 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=93882953&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 93882953 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: 1/8/2014 vid: 136 iid: 1 pid: 997 pub: American Chemical Society artinfo: ui: 93882953 10.1021/ja411672f ppf: 495 ppct: 11 formats: tig: atl: Self-Association and Nitroaromatic-Induced Deaggregation of Pyrene Substituted Pyridine Amides. aug: au: Sung Kuk Kim Jong Min Lim Tuhin Pradhan Hyo Sung Jung Lynch, Vincent M. Jong Seung Kim Dongho Kim Sessler, Jonathan L. affil: Department of Chemistry, The University of Texas at Austin, 105 East 24th Street, Stop A5300, Austin, Texas 78712-1224, United States Department of Chemistry, Yonsei University, Seoul 120-749, Korea Department of Chemistry, Korea University, Seoul 136-701, Korea su: Density functionals Chlorohydrocarbons Trihalomethanes Aromatic compounds Organic compounds sug: subj: Density functionals Chlorohydrocarbons Trihalomethanes Aromatic compounds Organic compounds ab: The self-assembly features of the bis-pyrene methyl amide functionalized pyridine and benzene "tweezers" 1 and 2 were studied in organic solution and in the solid state. These systems were found to display remarkably different selfassociation features and optical properties, which was rationalized by control experiments using compounds bearing pyrenemethyl esters, alkyl groups, or a single pyrene substituent (3-6). As dilute solutions in chloroform, tweezers 1 displays both pyrene monomer and excimer emission features reflecting intramolecular contacts between the pyrene subunits. At higher concentrations in chloroform, as well as in the solid state, tweezers 1 self-assembles to form a linear supramolecular polymer. In contrast, tweezers 2 does not interact in an intermolecular fashion and photoexcitation produces emission features characteristic of a pyrene monomer. DFT (density functional theory) and TDDFT (time dependent density functional theory) calculations revealed that the lowest vertical transitions are forbidden and that S of 1 is an emissive state. In contrast to 1 and 2, both pyrene-free control systems 5 and 6 were found to form linearly self-assembled supramolecular arrays in the solid state, albeit of differing structure. Upon exposure to trinitrobenzene (TNB), the self-assembled structures formed from 1 undergo deaggregation to form TNB complexes. This change is reflected in both an easily discernible color change and a quenching of the fluorescence emission intensity. Changes in the optical features were also seen in the case of 2. However, notable differences between these two ostensibly similar systems were seen. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2014 holdings: @attributes: islocal: N |
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