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Volumn 49, Issue 35, 2010, Pages 6101-6105

Oligomers and cyclooligomers of rigid phenylene-ethynylene-butadiynylenes: Synthesis and self-assembled monolayers

Author keywords

Gel permeation chromatography; Glaser coupling; Macrocycles; Scanning probe microscopy; Self assembled monolayers

Indexed keywords

ADSORPTION BEHAVIOR; COPPER CATALYSIS; CYCLIC OLIGOMERS; GLASER COUPLING; MACROCYCLES; REACTION CONDITIONS; SCANNING PROBES; STM IMAGES;

EID: 77956040800     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201001625     Document Type: Article
Times cited : (27)

References (74)
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    • For recent publications about SAMs of shape-persistent linear coupling products see, e.g.
    • For recent publications about SAMs of shape-persistent linear coupling products see, e.g.: a) P. Samorí, N. Severin, K. Müllen, J. P. Rabe, Adv. Mater. 2000, 12, 579;
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    • Freely jointed chains are rigid segments of fixed length, interconnected by linkers that allow variable valence angles and rotation. In contrast, the hinges of freely rotating chains enforce fixed angles between adjacent segments, whilst still allowing free rotation with all torsion angles being equally likely. After adsorption to the substrate, the rotation is restricted, and the linked units may adopt cisoidal and transoidal conformation
    • Freely jointed chains are rigid segments of fixed length, interconnected by linkers that allow variable valence angles and rotation. In contrast, the hinges of freely rotating chains enforce fixed angles between adjacent segments, whilst still allowing free rotation with all torsion angles being equally likely. After adsorption to the substrate, the rotation is restricted, and the linked units may adopt cisoidal and transoidal conformation.
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    • Tobe could specifically couple bisacetylenes to form the acyclic oligomers under Hay conditions, whereas cyclic oligomers were formed under Eglinton contitions; see
    • Tobe could specifically couple bisacetylenes to form the acyclic oligomers under Hay conditions, whereas cyclic oligomers were formed under Eglinton contitions; see: Y. Tobe, N. Utsumi, A. Nagano, M. Sonoda, K. Naemura, Tetrahedron 2001, 57, 8075.
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    • The ratio of TMEDA to CuCl is of high importance for the reaction. With an excess of TMEDA, halogenation of the acetylenes was observed (see Supporting Information); see also
    • The ratio of TMEDA to CuCl is of high importance for the reaction. With an excess of TMEDA, halogenation of the acetylenes was observed (see Supporting Information); see also: T. Hamada, X. Ye, S. S. Stahl, J. Am. Chem. Soc. 2008, 130, 833.
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    • 2 as catalyst/oxidant mixture and pyridine as solvent were not successful, and only a dark brown tarry material of unknown composition could be isolated. The absence of cyclodimers was surprising, as the same coupling conditions worked well in most of our acetylene coupling reactions and gave (with a similar but smaller substrate) high to nearly quantitative product yields; see
    • 2 as catalyst/oxidant mixture and pyridine as solvent were not successful, and only a dark brown tarry material of unknown composition could be isolated. The absence of cyclodimers was surprising, as the same coupling conditions worked well in most of our acetylene coupling reactions and gave (with a similar but smaller substrate) high to nearly quantitative product yields; see: N. Shabelina, S. Klyatskaya, V. Enkelmann, S. Höger, C. R. Chim. 2009, 12, 430.
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    • Opris et al. also obtained cyclic products when bipyridyl containing bis(acetylene)s were oxidatively coupled under copper catalysis
    • Opris et al. also obtained cyclic products when bipyridyl containing bis(acetylene)s were oxidatively coupled under copper catalysis: D. M. Opris, A. Ossenbach, D. Lentz, A. D. Schlüter, Org. Lett. 2008, 10, 2091.
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    • Similarly, Kim et al. obtained rectangular shapepersistent macrocycles under copper catalysis; see
    • Similarly, Kim et al. obtained rectangular shapepersistent macrocycles under copper catalysis; see: J.-K. Kim, E. Lee, M.-C. Kim, E. Sim, M. Lee, J. Am. Chem. Soc. 2009, 131, 17768.
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    • 1b and 4b were not investigated under the conditions of the copper-catalyzed reaction
    • 1b and 4b were not investigated under the conditions of the copper-catalyzed reaction.
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    • 2 was identified when 4b was coupled under palladium catalysis; higher oligomers were not characterized
    • 2 was identified when 4b was coupled under palladium catalysis; higher oligomers were not characterized.
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    • Considering 1b and 4b with 2-ethylhexyloxy side chains, solubility is clearly not responsible for the observed discrimination between cyclic and acyclic products
    • Considering 1b and 4b with 2-ethylhexyloxy side chains, solubility is clearly not responsible for the observed discrimination between cyclic and acyclic products.
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    • 2 show the exact masses for the proposed structures
    • 2 show the exact masses for the proposed structures.
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    • 2 decomposes at > 325°C; see, and Ref. [10]
    • 2 decomposes at > 325°C; see: H. A. Staab, H. Bräumling, K. Schneider, Chem. Ber. 1968, 101, 879, and Ref. [10].
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    • For theoretical descriptions of the contrast mechanism in STM, see for example
    • For theoretical descriptions of the contrast mechanism in STM, see for example: a) R. Lazzaroni,A. Calderone, J. L. Brédas, J. P. Rabe, J. Chem. Phys. 1997, 107, 99;
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    • 2 on HOPG is rather expected instead of peculiar.
    • 2 on HOPG is rather expected instead of peculiar.
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    • -1; O-shaped polymorph: a=3.8±0.1 nm, b=2.7±0.1 nm, γ= 68±2°; S-shaped polymorph: a=3.6±0.1 nm, b=2.7±0.1 nm, γ=90±2°
    • -1; O-shaped polymorph: a=3.8±0.1 nm, b=2.7±0.1 nm, γ= 68±2°; S-shaped polymorph: a=3.6±0.1 nm, b=2.7±0.1 nm, γ=90±2°.
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    • 13 in this case) cannot be resolved by STM under the applied conditions, their orientation shall not be further discussed herein
    • 13 in this case) cannot be resolved by STM under the applied conditions, their orientation shall not be further discussed herein.
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    • For SAMs of alkanes on HOPG, see for example, and references therein
    • For SAMs of alkanes on HOPG, see for example: T. Yang, S. Berber, J.-F. Liu, G. P. Miller, D. Tománek, J. Chem. Phys. 2008, 128, 124709, and references therein.
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    • -1, annealed to 60°C for 2 min, unit cell: a = 8.2 ± 0.2 nm, b = 3.8 ± 0.1 nm, γ = 90 ± 2°)
    • n (n = 3, 5) are larger than for the respective even oligomers (n = 4, 6). All images were calibrated in situ using the HOPG substrate as reference grid (see the Supporting Information).


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