m-Diethynylbenzene macrocycles: Syntheses and self-association behavior in solution

Yoshito Tobe*, Naoto Utsumi, Kazuya Kawabata, Atsushi Nagano, Kiyomi Adachi, Shunji Araki, Motohiro Sonoda, Keiji Hirose, Koichiro Naemura

*Corresponding author for this work

Research output: Contribution to journalArticle

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Abstract

m-Diethynylbenzene macrocycles (DBMs), buta-1,3-diyne-bridged [4 n ]metacyclophanes, have been synthesized and their self-association behaviors in solution were investigated, Cyclic tetramers, hexamers, and octamers of DBMs having exo-annular octyl, hexadecyl, and 3,6,9-trioxadecyl ester groups were prepared by intermolecular oxidative coupling of dimer units or intramolecular cyclization of the corresponding open-chain oligomers. The aggregation properties were investigated by two methods, the 1 H NMR spectra and the vapor pressure osmometry (VPO). Although some discrepancies were observed between the association constants obtained from the two methods, the qualitative view was consistent with each other. The analysis of self-aggregation by VPO revealed unique aggregation behavior of DBMs in acetone and toluene, which was not elucidated by the NMR method. Namely, the association constants for infinite association are several times larger than the dimerization constant, suggesting that the aggregation is enhanced by the formation of dimers (a nucleation mechanism). In polar solvents, DBMs aggregate more strongly than in chloroform due to the solvophobic interactions between the macrocyclic framework and the solvents. Moreover, DBMs self-associate in aromatic solvents such as toluene and o-xylene more readily than in chloroform. In particular, the hexameric DBM having a large macrocyclic cavity exhibits extremely large association constants in aromatic solvents. By comparing the aggregation properties of DBMs with the corresponding acyclic oligomers, the effect of the macrocyclic structure on the aggregation propensity was clarified. Finally, it turned out that DBMs tend to aggregate more readily than the corresponding phenylacetylene macrocycles, acetylene-bridged [2 n ]metacyclophanes, owing to the withdrawal of the electron density from the aromatic rings by the butadiyne linkages which facilitates π-π stacking interactions.

Original languageEnglish
Pages (from-to)5350-5364
Number of pages15
JournalJournal of the American Chemical Society
Volume124
Issue number19
DOIs
StatePublished - 15 May 2002

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    Tobe, Y., Utsumi, N., Kawabata, K., Nagano, A., Adachi, K., Araki, S., Sonoda, M., Hirose, K., & Naemura, K. (2002). m-Diethynylbenzene macrocycles: Syntheses and self-association behavior in solution. Journal of the American Chemical Society, 124(19), 5350-5364. https://doi.org/10.1021/ja012458m