Using hinged ligands to target structurally flexible copper(ii) MOFs

Bloch, Witold M.; Doonan, Christian J.; Sumby, Christopher J.

doi:10.1039/c3ce41244j

Cited by 29 publications

(24 citation statements)

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“…20 The versatility and potential of the pyrazole-benzoate synthon is also seen by the incorporation into methylene 'hinged' bispyrazole-benzoate ligands to successfully target flexible MOFs. 21,22 In this paper we report the structures of H 2 L and its nitrate salt and describe the syntheses, structures and thermal studies of coordination networks and hydrogen-bonded networks of metal complexes of HL -.…”

Section: Introductionmentioning

confidence: 99%

The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid

et al. 2015

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. (2015). The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid. Dalton Transactions: an international journal of inorganic chemistry, 44 (19), 9269-9280.The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid AbstractThe synthesis, structural and thermal characterisation of a number of coordination complexes featuring the N,O-heteroditopic ligand 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoate, HL are reported. The reaction of H2L with cobalt(II) and nickel(II) nitrates at room temperature in basic DMF/H2O solution gave discrete mononuclear coordination complexes with the general formula {[M(HL)2(H2O)4]·2DMF} (M = Co (1), Ni (2)), whereas the reaction with zinc(II) nitrate gave [Zn(HL)2]∞, 3, a coordination polymer with distorted diamondoid topology and fourfold interpenetration. Coordination about the tetrahedral Zn(II) nodes in 3 are furnished by two pyrazolyl nitrogen atoms and two carboxylate oxygen atoms to give a mixed N2O2 donor set. The desolvation of 8 was followed by powder X-ray diffraction and single crystal X-ray diffraction which show desolvation induces the transition to a more closely packed structure while the coordination geometry about the copper ions and the network topology is retained. Powder X-ray diffraction and microanalysis were used to characterise the bulk purity of the coordination materials 1-6 and 8. The thermal characteristics of 1-2, 4-6 and 8 were studied by TG-DTA. This led to the curious observation of small exothermic events in networks 4, 6, and 8 that appear to be linked to their decomposition. In addition, the solid state structures of H2L and that of its protonated salt, H2L·HNO3, were also determined and revealed that H2L forms a 2-D hydrogen bonded polymer incorporating helical chains formed through N-HO and O-HN interactions, and that [H3L]NO3 forms a 1-D hydrogen-bonded polymer. The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid donor sets with trans-square planar geometry and is fourfold interpenetrated. The desolvation of 8 was followed by powder X-ray diffraction and single crystal X-ray diffraction which show desolvation induces the transition to a more closely packed structure while the coordination geometry about the copper ions and the network topology is retained. Powder X-ray diffraction and microanalysis were used to characterise the bulk purity of the coordination materials 1-6 and 8. The thermal characteristics of 1-2, 4-6 and 8 were studied by TG-DTA. This led to the curious observation of small exothermic events in networks 4, 6, and 8 that appear to be linked to their decomposition. In addition, the solid state structures of H 2 L and that of its protonated salt, H 2 L•HNO 3 , were also determined and revealed that H

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Section: Introductionmentioning

confidence: 99%

The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid

et al. 2015

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“…the materials retain 3rd generation behavior. [3][4][5] Based on previous studies, [20][21][22] it is likely that the gating originates from a trellislike structural change, i.e. expansion in one axis across the diamond-shaped pores and contraction across the other.…”

Section: Crystal Structuresmentioning

confidence: 99%

“…Motivated by the desirable properties of [Cu(bcppm)(H 2 O)], 22 here we demonstrate a strategy to covalently connect 2D MOFs by ligand design; i.e. synthetically installing a carbon-carbon connection between the 'hinges' of two equivalents of our flexible ligands [20][21][22] as a linking point between layers. This required us to design a new 'hinged' link ( Figure 1b, L) that would facilitate covalent connection of 2D materials.…”

Section: Introductionmentioning

confidence: 99%

“…[17][18][19] Recently, we introduced a strategy to reliably form flexible MOFs by designing a family of flexible organic links that possess a central chelating site. [20][21][22] Coordination of this central site modulates the flexibility of the organic link and gives rise to materials that routinely show 3rd generation behaviour. For example, a flexible silver(I) 3D material was formed using di-2-pyrazinylmethane (dpzm) as the organic building block; the material underwent solvent-induced expansion and contraction (breathing) upon exposure to different solvents.…”

Section: Introductionmentioning

confidence: 99%

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Utilising hinged ligands in MOF synthesis: a covalent linking strategy for forming 3D MOFs

2014

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Author DepositionAllowed Deposition by the author(s) When the author accepts the exclusive Licence to Publish for a journal article, he/she retains certain rights concerning the deposition of the whole article. He/she may: Deposit the accepted version of the submitted article in their institutional repository(ies).There shall be an embargo of making the above deposited material available to the public of 12 months from the date of acceptance. There shall be a link from this article to the PDF of the final published article on the RSC's website once this final version is available. May 2016Journal Name K however, due to the larger pore sizes molecular sieving of CO 2 /N 2 was not observed. Reaction of L with cobalt(II) gave a 3D hydrogen-bonded network incorporating 1D coordination polymer chains that is topologically equivalent to the Zn and Cd MOFs. The strategy outlined here demonstrates a novel route for designing more chemically and thermally robust 3D MOFs from 2D layered materials.

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“…The ligand bis(4-(4 -carboxyphenyl)-3,5-dimethyl-pyrazolyl)methane) (H 2 L) and MOF 1 were synthesized as previously reported [18]. All reagents were sourced from commercial vendors and used as received without further purification.…”

Section: Experimental Set-upmentioning

confidence: 99%

X-ray crystallographic insights into post-synthetic metalation products in a metal–organic framework

Huxley

Coghlan

Bloch

et al. 2017

Phil. Trans. R. Soc. A.

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ResearchCite this article: Huxley MT, Coghlan CJ, Bloch WM, Burgun A, Doonan CJ, Sumby CJ. 2017 X-ray crystallographic insights into post-synthetic metalation products in a metal-organic framework. Post-synthetic modification of metal-organic frameworks (MOFs) facilitates a strategic transformation of potentially inert frameworks into functionalized materials, tailoring them for specific applications. In particular, the postsynthetic incorporation of transition-metal complexes within MOFs, a process known as 'metalation', is a particularly promising avenue towards functionalizing MOFs. Herein, we describe the post-synthetic metalation of a microporous MOF with various transition-metal nitrates. The parent framework, 1, contains free-nitrogen donor chelation sites, which readily coordinate metal complexes in a single-crystal to single-crystal transformation which, remarkably, can be readily monitored by X-ray crystallography. The presence of an open void surrounding the chelation site in 1 prompted us to investigate the effect of the MOF pore environment on included metal complexes, particularly examining whether void space would induce changes in the coordination sphere of chelated complexes reminiscent of those found in the solution state. To test this hypothesis, we systematically metalated 1 with first-row transition-metal nitrates and elucidated the coordination environment of the respective transition-metal complexes using X-ray

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Using hinged ligands to target structurally flexible copper(ii) MOFs

Abstract: Using hinged ligands to target structurally flexible copper(II) MOFs Crystengcomm, 2013; 15(45):9663-9671

Cited by 29 publications

References 59 publications

The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid

The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid

Utilising hinged ligands in MOF synthesis: a covalent linking strategy for forming 3D MOFs

X-ray crystallographic insights into post-synthetic metalation products in a metal–organic framework

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