Rigid-strut-containing crown ethers and [2]catenanes for incorporation into metal-organic frameworks

To introduce crown ethers into the struts of metal–organic frameworks (MOFs), general approaches have been developed for the syntheses of dicarboxylic acid dibenzo[30]crown-10 (DB30C10DA), dicarboxylic acid di-2,3-naphtho[30]crown-10 (DN30C10DA), dicarboxylic acid bisparaphenylene[34]crown-10 (BPP34...

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Main Authors: Zhao, Yan-Li, Liu, Lihua, Zhang, Wenyu, Sue, Chi-Hau, Li, Qiaowei, Miljanić, Ognjen Š., Yaghi, Omar M., Stoddart, J. Fraser
Other Authors: School of Physical and Mathematical Sciences
Format: Article
Language:English
Published: 2014
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Online Access:https://hdl.handle.net/10356/106149
http://hdl.handle.net/10220/23961
http://dx.doi.org/10.1002/chem.200902350
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Institution: Nanyang Technological University
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spelling sg-ntu-dr.10356-1061492019-12-06T22:05:29Z Rigid-strut-containing crown ethers and [2]catenanes for incorporation into metal-organic frameworks Zhao, Yan-Li Liu, Lihua Zhang, Wenyu Sue, Chi-Hau Li, Qiaowei Miljanić, Ognjen Š. Yaghi, Omar M. Stoddart, J. Fraser School of Physical and Mathematical Sciences DRNTU::Science::Physics::Atomic physics::Properties of matter and antimatter To introduce crown ethers into the struts of metal–organic frameworks (MOFs), general approaches have been developed for the syntheses of dicarboxylic acid dibenzo[30]crown-10 (DB30C10DA), dicarboxylic acid di-2,3-naphtho[30]crown-10 (DN30C10DA), dicarboxylic acid bisparaphenylene[34]crown-10 (BPP34C10DA), and dicarboxylic acid 1,5-naphthoparaphenylene[36]crown-10 (NPP36C10DA). These novel crown ethers not only retain the characteristics of their parent crown ethers since they can 1) bind cationic guests and 2) serve as templates for making mechanically interlocked molecules (MIMs), such as catenanes and rotaxanes, but they also present coordination sites to connect with secondary building units (SBUs) in MOFs. The binding behavior of BPP34C10DA with 1,1′-dimethyl-4,4′-bipyridinium bis(hexafluorophosphate) (DMBP⋅2 PF6) has been investigated by means of UV/Vis, fluorescence, and NMR spectroscopic techniques. The crystal superstructure of the complex DMBP⋅2 PF6⊂ BPP34C10DA was determined by X-ray crystallography. The NPP36C10DA-based [2]catenane (H2NPP36C10DC-CAT⋅4 PF6) and the BPP34C10DA-based [2]catenane (H2BPP34C10DC-CAT⋅4 PF6) were prepared in DMF at room temperature by the template-directed clipping reactions of the planarly chiral NPP36C10DA and BPP34C10DA with 1,1′-[1,4-phenylenebis(methylene)]di-4,4′-bipyridin-1-ium bis(hexafluorophosphate) and 1,4-bis(bromomethyl)benzene, respectively. The crystal structure of the dimethyl ester (BPP34C10DE-CAT⋅4 PF6) of the [2]catenane H2BPP34C10DC-CAT⋅4 PF6 was investigated by X-ray crystallography, which revealed racemic R and S isomers with planar chirality present in the crystal in a 1:1 ratio. These crown ether based struts serve as excellent organic ligands to bind with transition metal ions in the construction of MOFs: the crown ethers BPP34C10DA and NPP36C10DA in the presence of Zn(NO3)2⋅4 H2O afforded the MOF-1001 and MOF-1002 frameworks, respectively. The crystal structures of MOF-1001 and MOF-1002 are both cubic and display Fmequation imagem symmetry. The unit cell parameter of the metal–organic frameworks is a=52.9345 Å. Since such MOFs, containing electron-donating crown ethers are capable of docking incoming electron-accepting substrates in a stereoelectronically controlled fashion, the present work opens a new access to the preparation and application of MOFs. 2014-10-07T01:25:22Z 2019-12-06T22:05:29Z 2014-10-07T01:25:22Z 2019-12-06T22:05:29Z 2009 2009 Journal Article Zhao, Y. L., Liu, L., Zhang, W., Sue, C. H., Li, Q., Miljanić, O., Yaghi, O.,& Stoddart, J. (2009). Rigid-strut-containing crown ethers and [2]catenanes for incorporation into metal-organic frameworks. Chemistry - a European journal, 15(48), 13356-13380. 0947-6539 https://hdl.handle.net/10356/106149 http://hdl.handle.net/10220/23961 http://dx.doi.org/10.1002/chem.200902350 159762 en Chemistry - a European journal © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
institution Nanyang Technological University
building NTU Library
country Singapore
collection DR-NTU
language English
topic DRNTU::Science::Physics::Atomic physics::Properties of matter and antimatter
spellingShingle DRNTU::Science::Physics::Atomic physics::Properties of matter and antimatter
Zhao, Yan-Li
Liu, Lihua
Zhang, Wenyu
Sue, Chi-Hau
Li, Qiaowei
Miljanić, Ognjen Š.
Yaghi, Omar M.
Stoddart, J. Fraser
Rigid-strut-containing crown ethers and [2]catenanes for incorporation into metal-organic frameworks
description To introduce crown ethers into the struts of metal–organic frameworks (MOFs), general approaches have been developed for the syntheses of dicarboxylic acid dibenzo[30]crown-10 (DB30C10DA), dicarboxylic acid di-2,3-naphtho[30]crown-10 (DN30C10DA), dicarboxylic acid bisparaphenylene[34]crown-10 (BPP34C10DA), and dicarboxylic acid 1,5-naphthoparaphenylene[36]crown-10 (NPP36C10DA). These novel crown ethers not only retain the characteristics of their parent crown ethers since they can 1) bind cationic guests and 2) serve as templates for making mechanically interlocked molecules (MIMs), such as catenanes and rotaxanes, but they also present coordination sites to connect with secondary building units (SBUs) in MOFs. The binding behavior of BPP34C10DA with 1,1′-dimethyl-4,4′-bipyridinium bis(hexafluorophosphate) (DMBP⋅2 PF6) has been investigated by means of UV/Vis, fluorescence, and NMR spectroscopic techniques. The crystal superstructure of the complex DMBP⋅2 PF6⊂ BPP34C10DA was determined by X-ray crystallography. The NPP36C10DA-based [2]catenane (H2NPP36C10DC-CAT⋅4 PF6) and the BPP34C10DA-based [2]catenane (H2BPP34C10DC-CAT⋅4 PF6) were prepared in DMF at room temperature by the template-directed clipping reactions of the planarly chiral NPP36C10DA and BPP34C10DA with 1,1′-[1,4-phenylenebis(methylene)]di-4,4′-bipyridin-1-ium bis(hexafluorophosphate) and 1,4-bis(bromomethyl)benzene, respectively. The crystal structure of the dimethyl ester (BPP34C10DE-CAT⋅4 PF6) of the [2]catenane H2BPP34C10DC-CAT⋅4 PF6 was investigated by X-ray crystallography, which revealed racemic R and S isomers with planar chirality present in the crystal in a 1:1 ratio. These crown ether based struts serve as excellent organic ligands to bind with transition metal ions in the construction of MOFs: the crown ethers BPP34C10DA and NPP36C10DA in the presence of Zn(NO3)2⋅4 H2O afforded the MOF-1001 and MOF-1002 frameworks, respectively. The crystal structures of MOF-1001 and MOF-1002 are both cubic and display Fmequation imagem symmetry. The unit cell parameter of the metal–organic frameworks is a=52.9345 Å. Since such MOFs, containing electron-donating crown ethers are capable of docking incoming electron-accepting substrates in a stereoelectronically controlled fashion, the present work opens a new access to the preparation and application of MOFs.
author2 School of Physical and Mathematical Sciences
author_facet School of Physical and Mathematical Sciences
Zhao, Yan-Li
Liu, Lihua
Zhang, Wenyu
Sue, Chi-Hau
Li, Qiaowei
Miljanić, Ognjen Š.
Yaghi, Omar M.
Stoddart, J. Fraser
format Article
author Zhao, Yan-Li
Liu, Lihua
Zhang, Wenyu
Sue, Chi-Hau
Li, Qiaowei
Miljanić, Ognjen Š.
Yaghi, Omar M.
Stoddart, J. Fraser
author_sort Zhao, Yan-Li
title Rigid-strut-containing crown ethers and [2]catenanes for incorporation into metal-organic frameworks
title_short Rigid-strut-containing crown ethers and [2]catenanes for incorporation into metal-organic frameworks
title_full Rigid-strut-containing crown ethers and [2]catenanes for incorporation into metal-organic frameworks
title_fullStr Rigid-strut-containing crown ethers and [2]catenanes for incorporation into metal-organic frameworks
title_full_unstemmed Rigid-strut-containing crown ethers and [2]catenanes for incorporation into metal-organic frameworks
title_sort rigid-strut-containing crown ethers and [2]catenanes for incorporation into metal-organic frameworks
publishDate 2014
url https://hdl.handle.net/10356/106149
http://hdl.handle.net/10220/23961
http://dx.doi.org/10.1002/chem.200902350
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