Capturing snapshots of post-synthetic metallation chemistry in metal–organic frameworks

Bloch, Witold M.; Burgun, Aléxandre; Coghlan, Campbell J.; Lee, Richmond; Coote, Michelle L.; Doonan, Christian J.; Sumby, Christopher J.

doi:10.1038/nchem.2045

Cited by 182 publications

(172 citation statements)

References 43 publications

Supporting

Mentioning

163

Contrasting

Unclassified

Order By: Relevance

“…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

View full text Add to dashboard Cite

. (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

show abstract

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

View full text Add to dashboard Cite

show abstract

“…Prior to discussing the preparation and characterisation of the new materials, we first briefly review the structural details of the parent Mn 3 L 3 structure type 7 that are relevant to the manipulations in the mixed-component systems. …”

Section: Resultsmentioning

confidence: 99%

“…The pores of the MOF contain a peak, assigned as a chloride (0.2 occupancy, 40%), to provide charge balance to the octahedral Fe centre, that sits in the pocket typically occupied by anions within the MOF structure. 7,13 There is additional electron density in this site (largest peak = 2.958 e·Å 3 , unmodeled before application of the SQUEEZE routine of Platon 15 ), which is potentially ascribable to a partial occupancy of solvent molecules occupying this position in the absence of an anion. Note that the ability of these bispyrazolate moieties to accommodate both Fe 2+ and Fe 3+ ions is of interest in catalytic processes involving redox transformations, and studies directed toward understanding the reactivity of these sites is currently underway.…”

Section: Structure Of Mn 3-x Fe X L 3 •04fecl 2 (X = 055)mentioning

confidence: 99%

“…7 This material features free bispyrazolate coordination sites that are available for post-synthetic metal insertions, providing the opportunity for the composition of the metal component to be tuned at both the metal node and at the bispyrazolate sites. Moreover, the incorporation of linkers with additional functionalisation at the periphery of the bispyrazolate moieties is also of interest for tuning the metal binding affinity, as well as the dynamic properties of the framework.…”

Section: Introductionmentioning

confidence: 99%

“…cations revealed full occupancy of the bispyrazolate binding sites under the same reaction conditions. 7 Therefore, we surmised that the decrease in Co 2+ uptake is a result of the L' linker being unable to accommodate metal species at its bispyrazolate moiety under these conditions. Further, the slope of the linear fit in Fig.…”

mentioning

confidence: 99%

See 2 more Smart Citations

Site-specific metal and ligand substitutions in a microporous Mn²⁺-based metal–organic framework

et al. 2016

Self Cite

View full text Add to dashboard Cite

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. March 2017 Dalton Transactions ARTICLE Please do not adjust marginsCentre for Advanced Nanomaterials, School of Physical Sciences, University of Adelaide, SA 5005, Australia. Email: kenji.sumida@adelaide.edu.au; christopher.sumby@adelaide.edu.au; christian.doonan@adelaide.edu.au. †Electronic Supplementary Information (ESI) available: Full experimental procedures, powder X-ray diffraction data, thermogravimetric analysis data, adsorption isotherms, and additional discussion. See DOI: 10.1039/x0xx00000x IntroductionMetal-organic frameworks (MOFs) 1 are an emerging class of porous materials that have received intensive investigation in recent years due to their high surface areas, and structural and chemical tunability. These features are attractive for a wide range of applications, including gas storage, molecular separations, heterogeneous catalysis, and their integration within functional devices.2 While the large library of MOFs now available to researchers encompass a broad range of properties, there is an increasing need for the development of techniques that facilitate molecular-level manipulations of their framework compositions to engender an even greater degree of control over the properties of the materials. In the area of mixed-metal and mixed-ligand MOFs, a number of preparative strategies have emerged that afford functionalised variants of existing structure types, and considerable effort has also been directed toward the discovery of unique structure types that depend on the mixed compositions for their assembly. These synthetic methods can generally be classified into direct synthetic methods that employ mixed-component reaction solutions, 3 Experimental SectionUnless otherwise stated, all preparations of the organic compounds were performed under an Ar atmosphere using standard Schlenk techniques with dried and degassed solvents. All MOF synthesis reactions were carried out in the air. All reagents except 4-bromo-bis(3,5-trifluoromethyl)pyrazole 8 were obtained from commercial vendors and used without further purification. Powder X-ray diffraction data were collected on a Bruker Advance D8 diffractometer equipped with a capillary stage using Cu Kα radiation (λ = 1.5418 Å). NMR spectra were recorded on a Varian 500 MHz spectrometer operating at 23 °C and equipped with a 5 mm probe. Thermogravimetric analysis was performed on a PerkinElmer STA-6000 instrument using a nitrogen flow. Adsorption isotherms were collect...

show abstract

Defective Metal‐Organic Frameworks

et al. 2018

View full text Add to dashboard Cite

The targeted incorporation of defects into crystalline matter allows for the manipulation of many properties and has led to relevant discoveries for optimized and even novel technological applications of materials. It is therefore exciting to see that defects are now recognized to be similarly useful in tailoring properties of metal-organic frameworks (MOFs). For instance, heterogeneous catalysis crucially depends on the number of active catalytic sites as well as on diffusion limitations. By the incorporation of missing linker and missing node defects into MOFs, both parameters can be accessed, improving the catalytic properties. Furthermore, the creation of defects allows for adding properties such as electronic conductivity, which are inherently absent in the parent MOFs. Herein, progress of the rapidly evolving field of the past two years is overviewed, putting a focus on properties that are altered by the incorporation and even tailoring of defects in MOFs. A brief account is also given on the emerging quantitative understanding of defects and heterogeneity in MOFs based on scale-bridging computational modeling and simulations.

show abstract

Capturing snapshots of post-synthetic metallation chemistry in metal–organic frameworks

Cited by 182 publications

References 43 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

Site-specific metal and ligand substitutions in a microporous Mn²⁺-based metal–organic framework

Defective Metal‐Organic Frameworks

Contact Info

Product

Resources

About

Capturing snapshots of post-synthetic metallation chemistry in metal–organic frameworks

Cited by 182 publications

References 43 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

Site-specific metal and ligand substitutions in a microporous Mn2+-based metal–organic framework

Defective Metal‐Organic Frameworks

Contact Info

Product

Resources

About

Site-specific metal and ligand substitutions in a microporous Mn²⁺-based metal–organic framework