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Title: Exploring New Assembly Modes of Uranyl Terephthalate: Templated Syntheses and Structural Regulation of a Series of Rare 2D → 3D Polycatenated Frameworks

In this paper, the reaction of uranyl nitrate with terephthalic acid (H 2TP) under hydrothermal conditions in the presence of an organic base, 1,3-(4,4'-bispyridyl)propane (BPP) or 4,4'-bipyridine (BPY), provided four uranyl terephthalate compounds with different entangled structures by a pH-tuning method. [UO 2(TP) 1.5](H 2BPP) 0.5·2H 2O (1) obtained in a relatively acidic solution (final aqueous pH, 4.28) crystallizes in the form of a noninterpenetrated honeycomb-like two-dimensional network structure. An elevation of the solution pH (final pH, 5.21) promotes the formation of a dimeric uranyl-mediated polycatenated framework, [(UO 2) 2(μ-OH) 2(TP) 2] 2(H 2BPP) 2·4.5H 2O (2). Another new polycatenated framework with a monomeric uranyl unit, [(UO 2) 2(TP) 3](H 2BPP) (3), begins to emerge as a minor accompanying product of 2 when the pH is increased up to 6.61, and turns out to be a significant product at pH 7.00. When more rigid but small-size BPY molecules replace BPP molecules, [UO 2(TP) 1.5](H 2BPP) 0.5 (4) with a polycatenated framework similar to 3 was obtained in a relatively acidic solution (final pH, 4.81). The successful preparation of 2–4 represents the first report of uranyl–organic polycatenated frameworks derived from a simple H 2TP linker. Finally, a direct comparison between thesemore » polycatenated frameworks and previously reported uranyl terephthalate compounds suggests that the template and cavity-filling effects of organic bases (such as BPP or BPY), in combination with specific hydrothermal conditions, promote the formation of uranyl terephthalate polycatenated frameworks.« less
Authors:
ORCiD logo [1] ;  [1] ;  [1] ;  [2] ;  [3] ; ORCiD logo [4] ; ORCiD logo [1]
  1. Chinese Academy of Sciences (CAS), Beijing (China). Lab. of Nuclear Energy Chemistry. Inst. of High Energy Physics
  2. Chinese Academy of Sciences (CAS), Beijing (China). Beijing Synchrotron Radiation Facility. Inst. of High Energy Physics
  3. Chinese Academy of Sciences (CAS), Beijing (China). Lab. of Nuclear Energy Chemistry. Inst. of High Energy Physics; Soochow Univ., Suzhou (China). School of Radiological and Interdisciplinary Sciences. Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Grant/Contract Number:
AC02-05CH11231; 21671191; 21577144; 11405186; 91426302; 91326202; JCKY2016212A504
Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 56; Journal Issue: 14; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Chinese Academy of Sciences (CAS), Beijing (China)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Natural Science Foundation of China (NNSFC); Ministry of Industry and Information Technology of China
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
OSTI Identifier:
1436634

Mei, Lei, Wang, Cong-zhi, Zhu, Liu-zheng, Gao, Zeng-qiang, Chai, Zhi-fang, Gibson, John K., and Shi, Wei-qun. Exploring New Assembly Modes of Uranyl Terephthalate: Templated Syntheses and Structural Regulation of a Series of Rare 2D → 3D Polycatenated Frameworks. United States: N. p., Web. doi:10.1021/acs.inorgchem.7b00312.
Mei, Lei, Wang, Cong-zhi, Zhu, Liu-zheng, Gao, Zeng-qiang, Chai, Zhi-fang, Gibson, John K., & Shi, Wei-qun. Exploring New Assembly Modes of Uranyl Terephthalate: Templated Syntheses and Structural Regulation of a Series of Rare 2D → 3D Polycatenated Frameworks. United States. doi:10.1021/acs.inorgchem.7b00312.
Mei, Lei, Wang, Cong-zhi, Zhu, Liu-zheng, Gao, Zeng-qiang, Chai, Zhi-fang, Gibson, John K., and Shi, Wei-qun. 2017. "Exploring New Assembly Modes of Uranyl Terephthalate: Templated Syntheses and Structural Regulation of a Series of Rare 2D → 3D Polycatenated Frameworks". United States. doi:10.1021/acs.inorgchem.7b00312. https://www.osti.gov/servlets/purl/1436634.
@article{osti_1436634,
title = {Exploring New Assembly Modes of Uranyl Terephthalate: Templated Syntheses and Structural Regulation of a Series of Rare 2D → 3D Polycatenated Frameworks},
author = {Mei, Lei and Wang, Cong-zhi and Zhu, Liu-zheng and Gao, Zeng-qiang and Chai, Zhi-fang and Gibson, John K. and Shi, Wei-qun},
abstractNote = {In this paper, the reaction of uranyl nitrate with terephthalic acid (H2TP) under hydrothermal conditions in the presence of an organic base, 1,3-(4,4'-bispyridyl)propane (BPP) or 4,4'-bipyridine (BPY), provided four uranyl terephthalate compounds with different entangled structures by a pH-tuning method. [UO2(TP)1.5](H2BPP)0.5·2H2O (1) obtained in a relatively acidic solution (final aqueous pH, 4.28) crystallizes in the form of a noninterpenetrated honeycomb-like two-dimensional network structure. An elevation of the solution pH (final pH, 5.21) promotes the formation of a dimeric uranyl-mediated polycatenated framework, [(UO2)2(μ-OH)2(TP)2]2(H2BPP)2·4.5H2O (2). Another new polycatenated framework with a monomeric uranyl unit, [(UO2)2(TP)3](H2BPP) (3), begins to emerge as a minor accompanying product of 2 when the pH is increased up to 6.61, and turns out to be a significant product at pH 7.00. When more rigid but small-size BPY molecules replace BPP molecules, [UO2(TP)1.5](H2BPP)0.5 (4) with a polycatenated framework similar to 3 was obtained in a relatively acidic solution (final pH, 4.81). The successful preparation of 2–4 represents the first report of uranyl–organic polycatenated frameworks derived from a simple H2TP linker. Finally, a direct comparison between these polycatenated frameworks and previously reported uranyl terephthalate compounds suggests that the template and cavity-filling effects of organic bases (such as BPP or BPY), in combination with specific hydrothermal conditions, promote the formation of uranyl terephthalate polycatenated frameworks.},
doi = {10.1021/acs.inorgchem.7b00312},
journal = {Inorganic Chemistry},
number = 14,
volume = 56,
place = {United States},
year = {2017},
month = {6}
}