Post-synthetic pore-space expansion in a di-tagged metal–organic framework

Tshering, Lodey; Hunter, Sally O.; Nikolich, Alexandra; Minato, Erica; Fitchett, Christopher M.; D’Alessandro, Deanna M.; Richardson, Christopher

doi:10.1039/c4ce01377h

Cited by 14 publications

(16 citation statements)

References 34 publications

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“…36,37 TG-DTA was used to observe the mass and thermal response of heating 1. The TG-DT measurement of activated 1 recorded under a flowing atmosphere of N 2 is shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

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Thermally-promoted post-synthetic Pummerer chemistry in a sulfoxide-functionalized metal–organic framework

Bryant

Richardson

2015

CrystEngComm

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. (2015). Thermally-promoted post-synthetic Pummerer chemistry in a sulfoxide-functionalized metalorganic framework. CrystEngComm, 17 (46), 8858-8863.Thermally-promoted post-synthetic Pummerer chemistry in a sulfoxidefunctionalized metal-organic framework AbstractReported herein is a thermally-promoted, post-synthetic modification of a zinc metal-organic frameworks pore surface. Sulfoxide tag groups are modified by conventional heating via Pummerer-type chemistry and elimination to aldehyde groups. Simultaneously, a minor competing disproportionation reaction occurs, creating sulfide and sulfone tag groups enhancing the complexity of the pores. The thermal process is gentle, with crystallinity fully maintained, and results in a higher surface area and pore volume for the modified framework.

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“…36,37 TG-DTA was used to observe the mass and thermal response of heating 1. The TG-DT measurement of activated 1 recorded under a flowing atmosphere of N 2 is shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

“…36,37 One benefit of this approach is avoiding chemical reagents in the post-synthetic step as all that is required is 'front loaded' in direct synthesis. In this article we report on the thermally-promoted reactions of ligands bearing sulfoxide tag groups in MOFs.…”

Section: -13mentioning

confidence: 99%

Thermally-promoted post-synthetic Pummerer chemistry in a sulfoxide-functionalized metal–organic framework

Bryant

Richardson

2015

CrystEngComm

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“…33,34 The DT-TGA of 'as synthesized' WUF-1, recorded under an atmosphere of N 2 , is shown in Figure 2 (Figures S10 and S11), confirming the intact nature of the bridging ligands. Of particular note is the very clean and very high conversion of this PSR and the simplicity and accessibility of conventional heating to achieve the modification.…”

Section: Post-synthetic Rearrangement and Characterizationmentioning

confidence: 73%

“…We utilized the little-known thermolysis of alkyl sulfoxides to generate aldehyde groups in MOFs via Pummerer-type chemistry. 32 Of particular interest to us are post-synthetic rearrangements (PSRs) and we have reported examples of reagentless PSRs based upon the aromatic Claisen rearrangement in solvent 33 and solventless procedures. 34 For this study, we prepared the bridging ligand 2-((dimethylcarbamothioyl)oxy)-[1,1'-biphenyl]-4,4'-dicarboxylic acid, H 2 L 1 .…”

Section: Introductionmentioning

confidence: 99%

High Temperature Postsynthetic Rearrangement of Dimethylthiocarbamate-Functionalized Metal–Organic Frameworks

Ablott

Turzer

Telfer

et al. 2016

Crystal Growth & Design

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. (2016). High temperature postsynthetic rearrangement of dimethylthiocarbamate-functionalized metal-organic frameworks. Crystal Growth and Design, 16 (12),[7067][7068][7069][7070][7071][7072][7073] High temperature postsynthetic rearrangement of dimethylthiocarbamatefunctionalized metal-organic frameworks AbstractA thermally promoted postsynthetic rearrangement has been performed on a zinc IRMOF-9-type framework bearing dimethylthiocarbamate tag groups. The rearrangement was accomplished via conventional heating at 285 °C. Crucially, despite the high temperature, the MOF maintains its high accessible surface area and pore space following thermal treatment. The structures and physical properties of the frameworks were characterized by a combination of single-crystal X-ray diffraction, powder X-ray diffraction, differential thermal-thermogravimetric analysis, and gas sorption analysis. The rearrangement results in a slightly higher level of CO 2 adsorption for the modified MOF but with equivalent heat of adsorption. This work offers new perspectives on postsynthetic rearrangements in MOFs and demonstrates that rearrangements that occur at relatively high temperatures are still compatible with the need to retain the structural integrity and porosity of the framework. A thermally-promoted post-synthetic rearrangement has been performed on a zinc IRMOF-9 type framework bearing dimethylthiocarbamate tag groups. The rearrangement was accomplished via conventional heating at 285 °C. Crucially, despite the high temperature, the MOF maintains its high accessible surface area and pore space following thermal treatment. The structures and physical properties of the frameworks were characterized by a combination of single X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), differential thermalthermogravimetric analysis (DT-TGA), and gas sorption analysis. The rearrangement results in a slightly higher level of CO 2 adsorption for the modified MOF but with equivalent heat of 2 adsorption. This work offers new perspectives on post-synthetic rearrangements in MOFs, and demonstrates that rearrangements that occur at relatively high temperatures are still compatible with the need to retain the structural integrity and porosity of the framework.

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“…We are involved in a programme of thermally-promoted post-synthetic modification of MOFs. [1][2][3][4] Provided that the requisite chemical functionality can be incorporated in the framework, thermally-promoted modifications are straightforward to implement as they simply require heating. Most modifications are eliminations and include thermolysis of tert-butoxycarbamates, [5][6][7] hemiaminals, 8 carboxylic acids, 9 and azides.…”

Section: Introductionmentioning

confidence: 99%

High temperature expulsion of thermolabile groups for pore-space expansion in metal–organic frameworks

et al. 2019

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Post-synthetic pore-space expansion in a di-tagged metal–organic framework

Cited by 14 publications

References 34 publications

Thermally-promoted post-synthetic Pummerer chemistry in a sulfoxide-functionalized metal–organic framework

Thermally-promoted post-synthetic Pummerer chemistry in a sulfoxide-functionalized metal–organic framework

High Temperature Postsynthetic Rearrangement of Dimethylthiocarbamate-Functionalized Metal–Organic Frameworks

High temperature expulsion of thermolabile groups for pore-space expansion in metal–organic frameworks

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