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Nano Research 2021, 14(2): 411-416 https://doi.org/10.1007/s12274-020-2873-y
Research Article | Issue | Published: 09 June 2020

Solid-state phase transformations toward a metal-organic framework of 7-connected Zn4O secondary building units

Show Author's Information Jaehui Kim,  Junsu Ha,  Jae Hwa Lee( ),  Hoi Ri Moon( )
Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea
Keywords:
metal-organic framework, secondary building units, solid-state transformation, linker basicity, ligand addition reaction
Topics:
MetalsOrganic frameworks Organic polymersOrganometallicsPorous materialsTopology
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Kim J, Ha J, Lee JH, et al. Solid-state phase transformations toward a metal-organic framework of 7-connected Zn4O secondary building units. Nano Research, 2021, 14(2): 411-416. https://doi.org/10.1007/s12274-020-2873-y
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Abstract Full text Electronic supplementary material About this article

In the development of metal-organic frameworks (MOFs), secondary building units (SBUs) have been utilized as molecular modules for the construction of nanoporous materials with robust structures. Under solvothermal synthetic conditions, dynamic changes in the metal coordination environments and ligand coordination modes of SBUs determine the resultant product structures. Alternatively, MOF phases with new topologies can also be achieved by post-synthetic treatment of as-synthesized MOFs via the introduction of acidic or basic moieties that cause the simultaneous cleavage/reformation of coordination bonds in the solid state. In this sense, we studied the solid-state transformation of two ndc-based Zn-MOFs (ndc = 1,4-naphthalene dicarboxylate) with different SBUs but the same pcu topology to another MOF with sev topology. One of the chosen MOFs with pcu nets is [Zn2(ndc)2(bpy)]n (bpy = 4,4’-bipyridine), (6Cbpy-MOF) consisting of a 6-connected pillared-paddlewheel SBU, and the other is IRMOF-7 composed of 6-connected Zn4O(COO)6 SBUs and ndc. Upon post-structural modification, these pcu MOFs were converted into the same MOF with sev topology constructed from the uncommon 7-connected Zn4O(COO)7 SBU (7C-MOF). The appropriate post-synthetic conditions for the transformation of each SBUs were systematically examined. In addition, the effect of the pillar molecules in the pillared-paddlewheel MOFs on the topology conversion was studied in terms of the linker basicity, which determines the inertness during the solid-state phase transformation. This post-synthetic modification approach is expected to expand the available methods for designing and synthesizing MOFs with controlled topologies.


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Electronic supplementary material
About this article

Solid-state phase transformations toward a metal-organic framework of 7-connected Zn4O secondary building units

Show Author's information Jaehui Kim, Junsu Ha, Jae Hwa Lee( ), Hoi Ri Moon( )
Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea

Abstract

In the development of metal-organic frameworks (MOFs), secondary building units (SBUs) have been utilized as molecular modules for the construction of nanoporous materials with robust structures. Under solvothermal synthetic conditions, dynamic changes in the metal coordination environments and ligand coordination modes of SBUs determine the resultant product structures. Alternatively, MOF phases with new topologies can also be achieved by post-synthetic treatment of as-synthesized MOFs via the introduction of acidic or basic moieties that cause the simultaneous cleavage/reformation of coordination bonds in the solid state. In this sense, we studied the solid-state transformation of two ndc-based Zn-MOFs (ndc = 1,4-naphthalene dicarboxylate) with different SBUs but the same pcu topology to another MOF with sev topology. One of the chosen MOFs with pcu nets is [Zn2(ndc)2(bpy)]n (bpy = 4,4’-bipyridine), (6Cbpy-MOF) consisting of a 6-connected pillared-paddlewheel SBU, and the other is IRMOF-7 composed of 6-connected Zn4O(COO)6 SBUs and ndc. Upon post-structural modification, these pcu MOFs were converted into the same MOF with sev topology constructed from the uncommon 7-connected Zn4O(COO)7 SBU (7C-MOF). The appropriate post-synthetic conditions for the transformation of each SBUs were systematically examined. In addition, the effect of the pillar molecules in the pillared-paddlewheel MOFs on the topology conversion was studied in terms of the linker basicity, which determines the inertness during the solid-state phase transformation. This post-synthetic modification approach is expected to expand the available methods for designing and synthesizing MOFs with controlled topologies.

Keywords: metal-organic framework, secondary building units, solid-state transformation, linker basicity, ligand addition reaction

References(42)

[1]
O. M. Yaghi,; M. J. Kalmutzki,; C. S. Diercks, Introduction to Reticular Chemistry: Metal-Organic Frameworks and Covalent Organic Frameworks; Wiley-VCH: Weinheim, 2019.
DOI
[2]
M. J. Kalmutzki,; N. Hanikel,; O. M. Yaghi, Secondary building units as the turning point in the development of the reticular chemistry of MOFs. Sci. Adv. 2018, 4, eaat9180.
DOI Google Scholar
[3]
D. J. Tranchemontagne,; J. L. Mendoza-Cortés,; M. O’Keeffe,; O. M. Yaghi, Secondary building units, nets and bonding in the chemistry of metal-organic frameworks. Chem. Soc. Rev. 2009, 38, 1257-1283.
DOI Google Scholar
[4]
J. S. Ha,; J. H. Lee,; H. R. Moon, Alterations to secondary building units of metal-organic frameworks for the development of new functions. Inorg. Chem. Front. 2020, 7, 12-27.
DOI Google Scholar
[5]
J. H. Lee,; S. Jeoung,; Y. G. Chung,; H. R. Moon, Elucidation of flexible metal-organic frameworks: Research progresses and recent developments. Coord. Chem. Rev. 2019, 389, 161-188.
DOI Google Scholar
[6]
A. V. Dighe,; R. Y. Nemade,; M. R. Singh, Modeling and simulation of crystallization of metal-organic frameworks. Processes 2019, 7, 527.
DOI Google Scholar
[7]
H. Aggarwal,; P. M. Bhatt,; C. X. Bezuidenhout,; L. J. Barbour, Direct evidence for single-crystal to single-crystal switching of degree of interpenetration in a metal-organic framework. J. Am. Chem. Soc. 2014, 136, 3776-3779.
DOI Google Scholar
[8]
R. J. Wei,; Q. Huo,; J. Tao,; R. B. Huang,; L. S. Zheng, Spin-crossover FeII4 squares: Two-step complete spin transition and reversible single-crystal-to-single-crystal transformation. Angew. Chem., Int. Ed. 2011, 50, 8940-8943.
DOI Google Scholar
[9]
X. P. Wang,; W. M. Chen,; H. Qi,; X. Y. Li,; C. Rajnák,; Z. Y. Feng,; M. Kurmoo,; R. Boča,; C. J. Jia,; C. H. Tung, et al. Solvent-controlled phase transition of a CoII-organic framework: From achiral to chiral and two to three dimensions. Chem.—Eur. J. 2017, 23, 7990-7996.
DOI Google Scholar
[10]
Z. H. Yan,; X. Y. Li,; L. W. Liu,; S. Q. Yu,; X. P. Wang,; D. Sun, Single-crystal to single-crystal phase transition and segmented thermochromic luminescence in a dynamic 3D interpenetrated AgI coordination network. Inorg. Chem. 2016, 55, 1096-1101.
DOI Google Scholar
[11]
S. Chaemchuen,; K. Zhou,; M. S. Yusubov,; P. S. Postnikov,; N. Klomkliang,; F. Verpoort, Solid-state transformation in porous metal-organic frameworks based on polymorphic-pillared net structure: Generation of tubular shaped MOFs. Micro. Meso. Mater. 2019, 278, 99-104.
Google Scholar
[12]
L. Schweighauser,; K. Harano,; E. Nakamura, Experimental study on interconversion between cubic MOF-5 and square MOF-2 arrays. Inorg. Chem. Commun. 2017, 84, 1-4.
Google Scholar
[13]
J. F. Xing,; L. Schweighauser,; S. Okada,; K. Harano,; E. Nakamura, Atomistic structures and dynamics of prenucleation clusters in MOF-2 and MOF-5 syntheses. Nat. Commun. 2019, 10, 3068.
Google Scholar
[14]
C. McKinstry,; E. J. Cussen,; A. J. Fletcher,; S. V. Patwardhan,; J. Sefcik, Effect of synthesis conditions on formation pathways of metal organic framework (MOF-5) crystals. Cryst. Growth Des. 2013, 13, 5481-5486.
Google Scholar
[15]
J. Kim,; M. R. Dolgos,; B. J. Lear, Isolation and chemical transformations involving a reactive intermediate of MOF-5. Cryst. Growth Des. 2015, 15, 4781-4786.
Google Scholar
[16]
G. Iannaccone,; A. Bernardi,; R. Suriano,; C. L. Bianchi,; M. Levi,; S. Turri,; G. Griffini, The role of sol-gel chemistry in the low-temperature formation of ZnO buffer layers for polymer solar cells with improved performance. RSC Adv. 2016, 6, 46915-46924.
Google Scholar
[17]
C. C. Yeh,; H. C. Liu,; W. Heni,; D. Berling,; H. W. Zan,; O. Soppera, Chemical and structural investigation of zinc-oxo cluster photoresists for DUV lithography. J. Mater. Chem. C 2017, 5, 2611-2619.
Google Scholar
[18]
K. Hirai,; J. Reboul,; N. Morone,; J. E. Heuser,; S. Furukawa,; S. Kitagawa, Diffusion-coupled molecular assembly: Structuring of coordination polymers across multiple length scales. J. Am. Chem. Soc. 2014, 136, 14966-14973.
Google Scholar
[19]
S. J. Lee,; C. Doussot,; A. Baux,; L. J. Liu,; G. B. Jameson,; C. Richardson,; J. J. Pak,; F. Trousselet,; F. X. Coudert,; S. G. Telfer, Multicomponent metal-organic frameworks as defect-tolerant materials. Chem. Mater. 2016, 28, 368-375.
Google Scholar
[20]
S. V. Beddoe,; R. F. Lonergan,; M. B. Pitak,; J. R. Price,; S. J. Coles,; J. A. Kitchen,; T. D. Keene, All about that base: Investigating the role of ligand basicity in pyridyl complexes derived from a copper-Schiff base coordination polymer. Dalton Trans. 2019, 48, 15553-15559.
Google Scholar
[21]
O. Karagiaridi,; W. Bury,; E. Tylianakis,; A. A. Sarjeant,; J. T. Hupp,; O. K. Farha, Opening metal-organic frameworks vol. 2: Inserting longer pillars into pillared-paddlewheel structures through solvent-assisted linker exchange. Chem. Mater. 2013, 25, 3499-3503.
Google Scholar
[22]
B. J. Burnett,; W. Choe, Stepwise pillar insertion into metal-organic frameworks: A sequential self-assembly approach. CrystEngComm 2012, 14, 6129-6131.
Google Scholar
[23]
S. Jeong,; D. Kim,; X. K. Song,; M. Choi,; N. Park,; M. S. Lah, Postsynthetic exchanges of the pillaring ligand in three-dimensional metal-organic frameworks. Chem. Mater. 2013, 25, 1047-1054.
Google Scholar
[24]
M. Misono, Heterogeneous Catalysis of Mixed Oxides: Perovskite and Heteropoly Catalysts; Elsevier: Oxford, 2013.
[25]
Y. Pan,; Q. J. Ding,; H. J. Xu,; C. Y. Shi,; A. Singh,; A. Kumar,; J. Q. Liu, A new Zn(II)-based 3D metal-organic framework with uncommon sev topology and its photocatalytic properties for the degradation of organic dyes. CrystEngComm 2019, 21, 4578-4585.
Google Scholar
[26]
S. Z. Bai,; W. Q. Zhang,; Y. Ling,; F. L. Yang,; M. L. Deng,; Z. X. Chen,; L. H. Weng,; Y. M. Zhou, Predicting and creating 7-connected Zn4O vertices for the construction of an exceptional metal-organic framework with nanoscale cages. CrystEngComm 2015, 17, 1923-1926.
Google Scholar
[27]
J. G. Duan,; M. Higuchi,; S. Kitagawa, Predesign and systematic synthesis of 11 highly porous coordination polymers with unprecedented topology. Inorg. Chem. 2015, 54, 1645-1649.
Google Scholar
[28]
Y. C. Qiu,; S. Yuan,; X. X. Li,; D. Y. Du,; C. Wang,; J. S. Qin,; H. F. Drake,; Y. Q. Lan,; L. Jiang,; H. C. Zhou, Face-sharing archimedean solids stacking for the construction of mixed-ligand metal-organic frameworks. J. Am. Chem. Soc. 2019, 141, 13841-13848.
Google Scholar
[29]
W. W. He,; S. L. Li,; G. S. Yang,; Y. Q. Lan,; Z. M. Su,; Q. Fu, Controllable synthesis of a non-interpenetrating microporous metal-organic framework based on octahedral cage-like building units for highly efficient reversible adsorption of iodine. Chem. Commun. 2012, 48, 10001-10003.
Google Scholar
[30]
D. B. Yu,; Q. Shao,; Q. J. Song,; J. W. Cui,; Y. L. Zhang,; B. Wu,; L. Ge,; Y. Wang,; Y. Zhang,; Y. Q. Qin, et al. A solvent-assisted ligand exchange approach enables metal-organic frameworks with diverse and complex architectures. Nat. Commun. 2020, 11, 927.
Google Scholar
[31]
M. Swain, Chemicalize.org. J. Chem. Inf. Model. 2012, 52, 613-615.
Google Scholar
[32]
B. L. Chen,; C. D. Liang,; J. Yang,; D. S. Contreras,; Y. L. Clancy,; E. B. Lobkovsky,; O. M. Yaghi,; S. Dai, A microporous metal-organic framework for gas-chromatographic separation of alkanes. Angew. Chem., Int. Ed. 2006, 45, 1390-1393.
Google Scholar
[33]
H. Chun,; D. N. Dybtsev,; H. Kim,; K. Kim, Synthesis, X-ray crystal structures, and gas sorption properties of pillared square grid nets based on paddle-wheel motifs: Implications for hydrogen storage in porous materials. Chem.—Eur. J. 2005, 11, 3521-3529.
Google Scholar
[34]
O. Shekhah,; H. Wang,; M. Paradinas,; C. Ocal,; B. Schüpbach,; A. Terfort,; D. Zacher,; R. A. Fischer,; C. Wöll, Controlling interpenetration in metal-organic frameworks by liquid-phase epitaxy. Nat. Mater. 2009, 8, 481-484.
Google Scholar
[35]
H. L. Jiang,; T. A. Makal,; H. C. Zhou, Interpenetration control in metal-organic frameworks for functional applications. Coord. Chem. Rev. 2013, 257, 2232-2249.
Google Scholar
[36]
M. L. Ding,; X. C. Cai,; H. L. Jiang, Improving MOF stability: Approaches and applications. Chem. Sci. 2019, 10, 10209-10230.
Google Scholar
[37]
L. D. Kong,; R. Y. Zou,; W. Z. Bi,; R. Q. Zhong,; W. J. Mu,; J. Liu,; R. P. S. Han,; R. Q. Zou, Selective adsorption of CO2/CH4 and CO2/N2 within a charged metal-organic framework. J. Mater. Chem. A 2014, 2, 17771-17778.
Google Scholar
[38]
J. Shang,; G. Li,; R. Singh,; Q. F. Gu,; K. M. Nairn,; T. J. Bastow,; N. Medhekar,; C. M. Doherty,; A. J. Hill,; J. Z. Liu, et al. Discriminative separation of gases by a “molecular trapdoor” mechanism in chabazite zeolites. J. Am. Chem. Soc. 2012, 134, 19246-19253.
Google Scholar
[39]
S. Guha,; S. Saha, Fluoride ion sensing by an anion-π interaction. J. Am. Chem. Soc. 2010, 132, 17674-17677.
Google Scholar
[40]
N. Hosono,; A. Terashima,; S. Kusaka,; R. Matsuda,; S. Kitagawa, Highly responsive nature of porous coordination polymer surfaces imaged by in situ atomic force microscopy. Nat. Chem. 2019, 11, 109-116.
Google Scholar
[41]
S Furukawa,; K. Hirai,; Y. Takashima,; K. Nakagawa,; M. Kondo,; T. Tsuruoka,; O. Sakata,; S. Kitagawa, A block PCP crystal: Anisotropic hybridization of porous coordination polymers by face-selective epitaxial growth. Chem. Commun. 2009, 5097-5099.
Google Scholar
[42]
N. L. Rosi,; J. Eckert,; M. Eddaoudi,; D. T. Vodak,; J. Kim,; M. O'Keeffe,; O. M. Yaghi, Hydrogen storage in microporous metal-organic frameworks. Science 2003, 300, 1127-1129.
Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 04 March 2020
Revised: 22 April 2020
Accepted: 11 May 2020
Published: 09 June 2020
Issue date: February 2021

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature

Acknowledgements

This work was supported by the National Research Foundation of Korea (NRF) Grant funded by the Ministry of Science and ICT (Nos. NRF-2016R1A5A1009405, NRF-2019M3E6A1103980, and NRF-2019R1A6A3A01096867).

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