A Hierarchical Nanoporous Diamondoid Superstructure

Guo, Qing-Hui; Liu, Zhichang; Li, Peng; Shen, Dengke; Xu, Yaobin; Ryder, Matthew R.; Chen, Haoyuan; Stern, Charlotte L.; Malliakas, Christos D.; Zhang, Xuan; Zhang, Lin; Qiu, Yunyan; Shi, Yi; Snurr, Randall Q.; Philp, Douglas; Farha, Omar K.; Stoddart, J. Fraser

doi:10.1016/j.chempr.2019.06.011

Title: A Hierarchical Nanoporous Diamondoid Superstructure

Abstract

Sophisticated architectures assembled from a single class of subunits by cooperative interactions are ubiquitous in nature. The construction of their artificial mimics, however, remains one of the most formidable challenges facing synthetic chemists. Here, we report a hierarchical diamondoid superstructure—namely, a supramolecular diamond—that is constructed from the multiple-level self-assembly of a highly symmetrical salt, hexakis[(4,4'-bipyridin-1-ium)methylene]benzene hexafluorophosphate. The uniform octahedral single crystals, with 96 cationic organic fragments and 96 counteranions in a unit cell, can be prepared quantitatively in a controllable one-step procedure within seconds at ambient conditions. The sizes of the resulting samples are modulated from 280 nm to 660 μm. The mechanism of the self-assembly was elucidated at the atomic level. As proof of its intrinsically cationic superstructure with mobile anions, the three-dimensional nanoporous framework can exchange efficiently with metal oxoanions. This research shows that precisely tunable hierarchical assemblies can translate charged molecules into complicated architectures.

Authors:: Guo, Qing-Hui; Liu, Zhichang; Li, Peng; Shen, Dengke; Xu, Yaobin; Ryder, Matthew R.; Chen, Haoyuan; Stern, Charlotte L.; Malliakas, Christos D.; Zhang, Xuan; Zhang, Lin; Qiu, Yunyan; Shi, Yi; Snurr, Randall Q.; Philp, Douglas; Farha, Omar K.; Stoddart, J. Fraser

Publication Date:: Sun Sep 01 00:00:00 EDT 2019

Research Org.:: Univ. of Notre Dame, IN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1660291

Alternate Identifier(s):: OSTI ID: 1544424; OSTI ID: 1561650

Grant/Contract Number:: NA0003763; FG02-08ER15967; AC02-05CH11231; AC05-00OR22725

Resource Type:: Published Article

Journal Name:: Chem

Additional Journal Information:: Journal Name: Chem Journal Volume: 5 Journal Issue: 9; Journal ID: ISSN 2451-9294

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 77 NANOSCIENCE AND NANOTECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; supramolecular diamond; diamondoid architecture; hierarchical self-assembly; nanoporous framework; metal oxoanion removal

Citation Formats


                    Guo, Qing-Hui, Liu, Zhichang, Li, Peng, Shen, Dengke, Xu, Yaobin, Ryder, Matthew R., Chen, Haoyuan, Stern, Charlotte L., Malliakas, Christos D., Zhang, Xuan, Zhang, Lin, Qiu, Yunyan, Shi, Yi, Snurr, Randall Q., Philp, Douglas, Farha, Omar K., and Stoddart, J. Fraser. A Hierarchical Nanoporous Diamondoid Superstructure.  United States: N. p., 2019. 
Web.  doi:10.1016/j.chempr.2019.06.011.

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                    Guo, Qing-Hui, Liu, Zhichang, Li, Peng, Shen, Dengke, Xu, Yaobin, Ryder, Matthew R., Chen, Haoyuan, Stern, Charlotte L., Malliakas, Christos D., Zhang, Xuan, Zhang, Lin, Qiu, Yunyan, Shi, Yi, Snurr, Randall Q., Philp, Douglas, Farha, Omar K., & Stoddart, J. Fraser. A Hierarchical Nanoporous Diamondoid Superstructure.  United States.  https://doi.org/10.1016/j.chempr.2019.06.011

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                    Guo, Qing-Hui, Liu, Zhichang, Li, Peng, Shen, Dengke, Xu, Yaobin, Ryder, Matthew R., Chen, Haoyuan, Stern, Charlotte L., Malliakas, Christos D., Zhang, Xuan, Zhang, Lin, Qiu, Yunyan, Shi, Yi, Snurr, Randall Q., Philp, Douglas, Farha, Omar K., and Stoddart, J. Fraser. Sun .  
"A Hierarchical Nanoporous Diamondoid Superstructure".  United States.  https://doi.org/10.1016/j.chempr.2019.06.011.

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@article{osti_1660291,

  title        = {A Hierarchical Nanoporous Diamondoid Superstructure},

  author       = {Guo, Qing-Hui and Liu, Zhichang and Li, Peng and Shen, Dengke and Xu, Yaobin and Ryder, Matthew R. and Chen, Haoyuan and Stern, Charlotte L. and Malliakas, Christos D. and Zhang, Xuan and Zhang, Lin and Qiu, Yunyan and Shi, Yi and Snurr, Randall Q. and Philp, Douglas and Farha, Omar K. and Stoddart, J. Fraser},

  abstractNote = {Sophisticated architectures assembled from a single class of subunits by cooperative interactions are ubiquitous in nature. The construction of their artificial mimics, however, remains one of the most formidable challenges facing synthetic chemists. Here, we report a hierarchical diamondoid superstructure—namely, a supramolecular diamond—that is constructed from the multiple-level self-assembly of a highly symmetrical salt, hexakis[(4,4'-bipyridin-1-ium)methylene]benzene hexafluorophosphate. The uniform octahedral single crystals, with 96 cationic organic fragments and 96 counteranions in a unit cell, can be prepared quantitatively in a controllable one-step procedure within seconds at ambient conditions. The sizes of the resulting samples are modulated from 280 nm to 660 μm. The mechanism of the self-assembly was elucidated at the atomic level. As proof of its intrinsically cationic superstructure with mobile anions, the three-dimensional nanoporous framework can exchange efficiently with metal oxoanions. This research shows that precisely tunable hierarchical assemblies can translate charged molecules into complicated architectures.},

  doi          = {10.1016/j.chempr.2019.06.011},

  journal      = {Chem},

  number       = 9,

  volume       = 5,

  place        = {United States},

  year         = {Sun Sep 01 00:00:00 EDT 2019},

  month        = {Sun Sep 01 00:00:00 EDT 2019}

}

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Figures / Tables:

Table 1: Summary of single-crystal structural features and electronic band gaps. See also Tables S2 and S7.

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