Self-Association and Nitroaromatic-Induced Deaggregation of Pyrene Substituted Pyridine Amides
- Authors
- Kim, Sung Kuk; Lim, Jong Min; Pradhan, Tuhin; Jung, Hyo Sung; Lynch, Vincent M.; Kim, Jong Seung; Kim, Dongho; Sesser, Jonathan L.
- Issue Date
- 8-1월-2014
- Publisher
- AMER CHEMICAL SOC
- Citation
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.136, no.1, pp.495 - 505
- Indexed
- SCIE
SCOPUS
- Journal Title
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
- Volume
- 136
- Number
- 1
- Start Page
- 495
- End Page
- 505
- URI
- https://scholar.korea.ac.kr/handle/2021.sw.korea/99549
- DOI
- 10.1021/ja411672f
- ISSN
- 0002-7863
- Abstract
- 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 self-association 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-1 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.
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