Selective Extraction of C70 by a Tetragonal Prismatic Porphyrin Cage

Yi Shi; Kang Cai; Hai Xiao; Zhichang Liu; Jiawang Zhou; Dengke Shen; Yunyan Qiu; Qing Hui Guo; Charlotte Stern; Michael R. Wasielewski; François Diederich; William A. Goddard; J. Fraser Stoddart

doi:10.1021/jacs.8b08555

Selective Extraction of C₇₀ by a Tetragonal Prismatic Porphyrin Cage

Yi Shi, Kang Cai, Hai Xiao, Zhichang Liu, Jiawang Zhou, Dengke Shen, Yunyan Qiu, Qing Hui Guo, Charlotte Stern, Michael R. Wasielewski, François Diederich, William A. Goddard, J. Fraser Stoddart^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

83 Scopus citations

Abstract

Along with the advent of supramolecular chemistry, research on fullerene receptors based on noncovalent bonding interactions has attracted a lot of attention. Here, we present the design and synthesis of a cationic molecular cage: a cyclophane composed of two tetraphenylporphyrins, bridged face-to-face by four viologen units in a rhomboid prismatic manner. The large cavity inside the cage, as well as the favorable donor-acceptor interactions between the porphyrin panels and the fullerene guests, enables the cage to be an excellent fullerene receptor. The 1:1 host-guest complexes formed between the cage and both C₆₀ and C₇₀ were characterized in solution by HRMS and NMR, UV-vis and fluorescence spectroscopies, and confirmed in the solid state by single-crystal X-ray diffraction analyses. The results from solution studies reveal that the cage has a much stronger binding for C₇₀ than for C₆₀, resulting in a selective extraction of C₇₀ from a C₆₀-enriched fullerene mixture (C₆₀/C₇₀ = 10/1), demonstrating the potential of the cage as an attractive receptor for fullerene separation.

Original language	English (US)
Pages (from-to)	13835-13842
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	140
Issue number	42
DOIs	https://doi.org/10.1021/jacs.8b08555
State	Published - Oct 24 2018

ASJC Scopus subject areas

Chemistry(all)
Biochemistry
Catalysis
Colloid and Surface Chemistry

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10.1021/jacs.8b08555

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@article{aabbc1eec2ba44c2976f2bcfaab99d9e,

title = "Selective Extraction of C70 by a Tetragonal Prismatic Porphyrin Cage",

abstract = "Along with the advent of supramolecular chemistry, research on fullerene receptors based on noncovalent bonding interactions has attracted a lot of attention. Here, we present the design and synthesis of a cationic molecular cage: a cyclophane composed of two tetraphenylporphyrins, bridged face-to-face by four viologen units in a rhomboid prismatic manner. The large cavity inside the cage, as well as the favorable donor-acceptor interactions between the porphyrin panels and the fullerene guests, enables the cage to be an excellent fullerene receptor. The 1:1 host-guest complexes formed between the cage and both C60 and C70 were characterized in solution by HRMS and NMR, UV-vis and fluorescence spectroscopies, and confirmed in the solid state by single-crystal X-ray diffraction analyses. The results from solution studies reveal that the cage has a much stronger binding for C70 than for C60, resulting in a selective extraction of C70 from a C60-enriched fullerene mixture (C60/C70 = 10/1), demonstrating the potential of the cage as an attractive receptor for fullerene separation.",

author = "Yi Shi and Kang Cai and Hai Xiao and Zhichang Liu and Jiawang Zhou and Dengke Shen and Yunyan Qiu and Guo, {Qing Hui} and Charlotte Stern and Wasielewski, {Michael R.} and Fran{\c c}ois Diederich and Goddard, {William A.} and {Fraser Stoddart}, J.",

note = "Funding Information: This research is part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdulaziz City of Science and Technology (KACST) and Northwestern University (NU). The authors thank both KACST and NU for their continued support of this research. Computational investigations were supported by the U.S. National Science Foundation under grant no. EFRI-1332411 (W.A.G. and H.X.). This work was also supported by the U.S. Department of Energy, Office of Science Office of Basic Energy Sciences under Award DE-FG02-99ER14999 (M.R.W. and J.Z.). Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

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doi = "10.1021/jacs.8b08555",

language = "English (US)",

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T1 - Selective Extraction of C70 by a Tetragonal Prismatic Porphyrin Cage

AU - Shi, Yi

AU - Cai, Kang

AU - Xiao, Hai

AU - Liu, Zhichang

AU - Zhou, Jiawang

AU - Shen, Dengke

AU - Qiu, Yunyan

AU - Guo, Qing Hui

AU - Stern, Charlotte

AU - Wasielewski, Michael R.

AU - Diederich, François

AU - Goddard, William A.

AU - Fraser Stoddart, J.

N1 - Funding Information: This research is part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdulaziz City of Science and Technology (KACST) and Northwestern University (NU). The authors thank both KACST and NU for their continued support of this research. Computational investigations were supported by the U.S. National Science Foundation under grant no. EFRI-1332411 (W.A.G. and H.X.). This work was also supported by the U.S. Department of Energy, Office of Science Office of Basic Energy Sciences under Award DE-FG02-99ER14999 (M.R.W. and J.Z.). Publisher Copyright: © 2018 American Chemical Society.

PY - 2018/10/24

Y1 - 2018/10/24

N2 - Along with the advent of supramolecular chemistry, research on fullerene receptors based on noncovalent bonding interactions has attracted a lot of attention. Here, we present the design and synthesis of a cationic molecular cage: a cyclophane composed of two tetraphenylporphyrins, bridged face-to-face by four viologen units in a rhomboid prismatic manner. The large cavity inside the cage, as well as the favorable donor-acceptor interactions between the porphyrin panels and the fullerene guests, enables the cage to be an excellent fullerene receptor. The 1:1 host-guest complexes formed between the cage and both C60 and C70 were characterized in solution by HRMS and NMR, UV-vis and fluorescence spectroscopies, and confirmed in the solid state by single-crystal X-ray diffraction analyses. The results from solution studies reveal that the cage has a much stronger binding for C70 than for C60, resulting in a selective extraction of C70 from a C60-enriched fullerene mixture (C60/C70 = 10/1), demonstrating the potential of the cage as an attractive receptor for fullerene separation.

AB - Along with the advent of supramolecular chemistry, research on fullerene receptors based on noncovalent bonding interactions has attracted a lot of attention. Here, we present the design and synthesis of a cationic molecular cage: a cyclophane composed of two tetraphenylporphyrins, bridged face-to-face by four viologen units in a rhomboid prismatic manner. The large cavity inside the cage, as well as the favorable donor-acceptor interactions between the porphyrin panels and the fullerene guests, enables the cage to be an excellent fullerene receptor. The 1:1 host-guest complexes formed between the cage and both C60 and C70 were characterized in solution by HRMS and NMR, UV-vis and fluorescence spectroscopies, and confirmed in the solid state by single-crystal X-ray diffraction analyses. The results from solution studies reveal that the cage has a much stronger binding for C70 than for C60, resulting in a selective extraction of C70 from a C60-enriched fullerene mixture (C60/C70 = 10/1), demonstrating the potential of the cage as an attractive receptor for fullerene separation.

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DO - 10.1021/jacs.8b08555

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SN - 0002-7863

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SP - 13835

EP - 13842

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 42

ER -

Selective Extraction of C₇₀ by a Tetragonal Prismatic Porphyrin Cage

Abstract

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CCDC 1840375: Experimental Crystal Structure Determination

CCDC 1840376: Experimental Crystal Structure Determination

CCDC 1840374: Experimental Crystal Structure Determination

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Selective Extraction of C70 by a Tetragonal Prismatic Porphyrin Cage

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CCDC 1840375: Experimental Crystal Structure Determination

CCDC 1840376: Experimental Crystal Structure Determination

CCDC 1840374: Experimental Crystal Structure Determination

Cite this

Selective Extraction of C₇₀ by a Tetragonal Prismatic Porphyrin Cage