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Nielsen MB, Schreiber M, Baek YG, et al. Highly functionalized dimeric tetraethynylethenes and expanded radialenes: strong evidence for macrocyclic cross-conjugation. Chemistry. 2001;7(15):3263-80doi: 10.1002/1521-3765(20010803)7:15<3263::aid-chem3263>3.0.co;2-3.
Nielsen, M. B., Schreiber, M., Baek, Y. G., Seiler, P., Lecomte, S., Boudon, C., Tykwinski, R. R., Gisselbrecht, J. P., Gramlich, V., Skinner, P. J., Bosshard, C., Günter, P., Gross, M., & Diederich, F. (2001). Highly functionalized dimeric tetraethynylethenes and expanded radialenes: strong evidence for macrocyclic cross-conjugation. Chemistry (Weinheim an der Bergstrasse, Germany), 7(15), 3263-80. https://doi.org/10.1002/1521-3765(20010803)7:15<3263::aid-chem3263>3.0.co;2-3
Nielsen, M B, et al. "Highly functionalized dimeric tetraethynylethenes and expanded radialenes: strong evidence for macrocyclic cross-conjugation." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 7,15 (2001): 3263-80. doi: https://doi.org/10.1002/1521-3765(20010803)7:15<3263::aid-chem3263>3.0.co;2-3
Nielsen MB, Schreiber M, Baek YG, Seiler P, Lecomte S, Boudon C, Tykwinski RR, Gisselbrecht JP, Gramlich V, Skinner PJ, Bosshard C, Günter P, Gross M, Diederich F. Highly functionalized dimeric tetraethynylethenes and expanded radialenes: strong evidence for macrocyclic cross-conjugation. Chemistry. 2001 Aug 03;7(15):3263-80. doi: 10.1002/1521-3765(20010803)7:15<3263::aid-chem3263>3.0.co;2-3. PMID: 11531112.
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Chemistry. 2001 Aug 03;7(15):3263-80. doi: 10.1002/1521-3765(20010803)7:15<3263::aid-chem3263>3.0.co;2-3.

Highly functionalized dimeric tetraethynylethenes and expanded radialenes: strong evidence for macrocyclic cross-conjugation.

Chemistry (Weinheim an der Bergstrasse, Germany)

M B Nielsen, M Schreiber, Y G Baek, P Seiler, S Lecomte, C Boudon, R R Tykwinski, J P Gisselbrecht, V Gramlich, P J Skinner, C Bosshard, P Günter, M Gross, F Diederich

Affiliations

  1. Laboratorium für Organische Chemie, ETH-Zentrum, Zürich, Switzerland.

PMID: 11531112 DOI: 10.1002/1521-3765(20010803)7:15<3263::aid-chem3263>3.0.co;2-3

Abstract

A selection of dimeric tetraethynylethenes (TEEs) and perethynylated expanded radialenes, containing different donor/acceptor substitution patterns, have been prepared and fully characterized. The first X-ray crystal structure of an expanded [6]radialene, with twelve peripheral 3,5-di(tert-butyl)phenyl substituents, is presented. This macrocycle, the all-carbon core of which is isomeric with fullerene C60, adopts a non-planar, "chair-like" conformation. Also a TEE dimer, carrying N,N-dimethylaniline donor substituents, has been subjected to an X-ray crystallographic analysis. The electronic properties were studied by UV/Vis spectroscopy and electrochemistry, providing fundamental insight into mechanisms of pi-electron delocalization in the acyclic and macrocyclic chromophores. Donor or donor-acceptor-substituted dimeric TEE derivatives show very strong absorptions extending over the entire UV/Vis region; their longest wavelength absorption bands have high charge-transfer character. Macrocyclic cross-conjugation in the expanded radialenes becomes increasingly efficient with increasing donor-acceptor polarization. A dual, strongly solvent-polarity-dependent fluorescence was observed for a tetrakis(N,N-dimethylaniline)-substituted dimeric TEE; this interesting emission behavior is explained by the twisted intramolecular charge-transfer (TICT) state model. Donor-substituted expanded radialenes display huge resonance-enhanced third-order nonlinear optical coefficients.

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