Understanding the structural landscape of Mn-based MOFs formed with hinged pyrazole carboxylate linkers

Josephine F. Smernik; Pol Gimeno-Fonquernie; Jorge Albalad; Tyla S. Jones; Rosemary J. Young; Neil R. Champness; Christian J. Doonan; Jack D. Evans; Christopher J. Sumby

doi:10.1039/D3CE00881A

Understanding the structural landscape of Mn-based MOFs formed with hinged pyrazole carboxylate linkers

Josephine F. Smernik, Pol Gimeno-Fonquernie, Jorge Albalad, Tyla S. Jones, Rosemary J. Young, Neil R. Champness, Christian J. Doonan, Jack D. Evans, Christopher J. Sumby

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Metal–organic frameworks (MOFs) capable of post-synthetic metalation (PSMet) have garnered significant interest as supports for catalytic metals. The Mn-based MOF, MnMOF-1 ([Mn₃(L2^Me)₃] where L2^Me = bis-(4-carboxyphenyl-3,5-dimethylpyrazolyl)methane), has been an exemplar for studying PSMet. Herein we investigate the synthesis of Mn-based MOFs from related flexible ditopic pyrazole carboxylate links, along with the formation of MOFs with similar tetratopic hinged linkers. We show for the first time that MnMOF-1 is likely a kinetic or metastable phase and a newly identified 2D layered material (MnMOF-2D) is the thermodynamically favoured product for this metal–linker combination. Formation of a MnMOF-1 structure with shorter linkers is thwarted by steric clashes that preclude the formation of the Mn3 cluster. This observation prompted the use of density functional theory (DFT) simulations that showed the target material to be very dense, highly strained and thereby energetically unfavourable, but potentially, a hypothetical MnMOF-1 structure with a longer phenylethynyl spacer would be energetically feasible. Finally, the predominance of 2D MOFs formed with shorter flexible links encouraged us to use tetratopic hinged linkers to form 3D frameworks, which was vindicated by the successful synthesis of two new porous 3D Mn-based MOFs, MnMOF-L4 and MnMOF-L5. These results highlight that reticular synthesis of MOFs formed with flexible, non-linear linkers is challenging.

Original language	English
Pages (from-to)	6539-6548
Number of pages	10
Journal	CrystEngComm
Volume	25
Issue number	47
Early online date	28 Sept 2023
DOIs	https://doi.org/10.1039/D3CE00881A
Publication status	Published - 21 Dec 2023

Bibliographical note

Acknowledgements:
C. J. S. and C. J. D. gratefully acknowledge the Australian Research Council for funding (DP190101402). J. D. E. was supported by a Ramsay Fellowship from the University of Adelaide and acknowledges an ARC DECRA fellowship (DE220100163). ZIH Dresden and Phoenix HPC service at the University of Adelaide are thanked for providing high-performance computing resources. This research was undertaken in part using the MX1 beamline at the Australian Synchrotron, part of ANSTO. J. F. S. and P. G.-F. gratefully acknowledge a Research Training Program Scholarship and University of Adelaide International Scholarship, respectively. P. G.-F. also acknowledges an Australian Institute of Nuclear Science and Technology Post-graduate Research Award. N. R. C. gratefully acknowledges support from the UK Engineering and Physical Sciences Research Council (EP/S002995/2).

Access to Document

10.1039/D3CE00881A

Complex-bearing Metal-Organic Frameworks: Snapshots of Reactions
Champness, N. (Principal Investigator)
Engineering & Physical Science Research Council
1/01/21 → 31/12/24
Project: Research Councils

Cite this

@article{f97fd496152246e28fe1a26fb6c87561,

title = "Understanding the structural landscape of Mn-based MOFs formed with hinged pyrazole carboxylate linkers",

abstract = "Metal–organic frameworks (MOFs) capable of post-synthetic metalation (PSMet) have garnered significant interest as supports for catalytic metals. The Mn-based MOF, MnMOF-1 ([Mn3(L2Me)3] where L2Me = bis-(4-carboxyphenyl-3,5-dimethylpyrazolyl)methane), has been an exemplar for studying PSMet. Herein we investigate the synthesis of Mn-based MOFs from related flexible ditopic pyrazole carboxylate links, along with the formation of MOFs with similar tetratopic hinged linkers. We show for the first time that MnMOF-1 is likely a kinetic or metastable phase and a newly identified 2D layered material (MnMOF-2D) is the thermodynamically favoured product for this metal–linker combination. Formation of a MnMOF-1 structure with shorter linkers is thwarted by steric clashes that preclude the formation of the Mn3 cluster. This observation prompted the use of density functional theory (DFT) simulations that showed the target material to be very dense, highly strained and thereby energetically unfavourable, but potentially, a hypothetical MnMOF-1 structure with a longer phenylethynyl spacer would be energetically feasible. Finally, the predominance of 2D MOFs formed with shorter flexible links encouraged us to use tetratopic hinged linkers to form 3D frameworks, which was vindicated by the successful synthesis of two new porous 3D Mn-based MOFs, MnMOF-L4 and MnMOF-L5. These results highlight that reticular synthesis of MOFs formed with flexible, non-linear linkers is challenging.",

author = "Smernik, {Josephine F.} and Pol Gimeno-Fonquernie and Jorge Albalad and Jones, {Tyla S.} and Young, {Rosemary J.} and Champness, {Neil R.} and Doonan, {Christian J.} and Evans, {Jack D.} and Sumby, {Christopher J.}",

note = "Acknowledgements: C. J. S. and C. J. D. gratefully acknowledge the Australian Research Council for funding (DP190101402). J. D. E. was supported by a Ramsay Fellowship from the University of Adelaide and acknowledges an ARC DECRA fellowship (DE220100163). ZIH Dresden and Phoenix HPC service at the University of Adelaide are thanked for providing high-performance computing resources. This research was undertaken in part using the MX1 beamline at the Australian Synchrotron, part of ANSTO. J. F. S. and P. G.-F. gratefully acknowledge a Research Training Program Scholarship and University of Adelaide International Scholarship, respectively. P. G.-F. also acknowledges an Australian Institute of Nuclear Science and Technology Post-graduate Research Award. N. R. C. gratefully acknowledges support from the UK Engineering and Physical Sciences Research Council (EP/S002995/2).",

year = "2023",

month = dec,

day = "21",

doi = "10.1039/D3CE00881A",

language = "English",

volume = "25",

pages = "6539--6548",

journal = "CrystEngComm",

issn = "1466-8033",

publisher = "Royal Society of Chemistry",

number = "47",

}

TY - JOUR

T1 - Understanding the structural landscape of Mn-based MOFs formed with hinged pyrazole carboxylate linkers

AU - Smernik, Josephine F.

AU - Gimeno-Fonquernie, Pol

AU - Albalad, Jorge

AU - Jones, Tyla S.

AU - Young, Rosemary J.

AU - Champness, Neil R.

AU - Doonan, Christian J.

AU - Evans, Jack D.

AU - Sumby, Christopher J.

N1 - Acknowledgements: C. J. S. and C. J. D. gratefully acknowledge the Australian Research Council for funding (DP190101402). J. D. E. was supported by a Ramsay Fellowship from the University of Adelaide and acknowledges an ARC DECRA fellowship (DE220100163). ZIH Dresden and Phoenix HPC service at the University of Adelaide are thanked for providing high-performance computing resources. This research was undertaken in part using the MX1 beamline at the Australian Synchrotron, part of ANSTO. J. F. S. and P. G.-F. gratefully acknowledge a Research Training Program Scholarship and University of Adelaide International Scholarship, respectively. P. G.-F. also acknowledges an Australian Institute of Nuclear Science and Technology Post-graduate Research Award. N. R. C. gratefully acknowledges support from the UK Engineering and Physical Sciences Research Council (EP/S002995/2).

PY - 2023/12/21

Y1 - 2023/12/21

N2 - Metal–organic frameworks (MOFs) capable of post-synthetic metalation (PSMet) have garnered significant interest as supports for catalytic metals. The Mn-based MOF, MnMOF-1 ([Mn3(L2Me)3] where L2Me = bis-(4-carboxyphenyl-3,5-dimethylpyrazolyl)methane), has been an exemplar for studying PSMet. Herein we investigate the synthesis of Mn-based MOFs from related flexible ditopic pyrazole carboxylate links, along with the formation of MOFs with similar tetratopic hinged linkers. We show for the first time that MnMOF-1 is likely a kinetic or metastable phase and a newly identified 2D layered material (MnMOF-2D) is the thermodynamically favoured product for this metal–linker combination. Formation of a MnMOF-1 structure with shorter linkers is thwarted by steric clashes that preclude the formation of the Mn3 cluster. This observation prompted the use of density functional theory (DFT) simulations that showed the target material to be very dense, highly strained and thereby energetically unfavourable, but potentially, a hypothetical MnMOF-1 structure with a longer phenylethynyl spacer would be energetically feasible. Finally, the predominance of 2D MOFs formed with shorter flexible links encouraged us to use tetratopic hinged linkers to form 3D frameworks, which was vindicated by the successful synthesis of two new porous 3D Mn-based MOFs, MnMOF-L4 and MnMOF-L5. These results highlight that reticular synthesis of MOFs formed with flexible, non-linear linkers is challenging.

AB - Metal–organic frameworks (MOFs) capable of post-synthetic metalation (PSMet) have garnered significant interest as supports for catalytic metals. The Mn-based MOF, MnMOF-1 ([Mn3(L2Me)3] where L2Me = bis-(4-carboxyphenyl-3,5-dimethylpyrazolyl)methane), has been an exemplar for studying PSMet. Herein we investigate the synthesis of Mn-based MOFs from related flexible ditopic pyrazole carboxylate links, along with the formation of MOFs with similar tetratopic hinged linkers. We show for the first time that MnMOF-1 is likely a kinetic or metastable phase and a newly identified 2D layered material (MnMOF-2D) is the thermodynamically favoured product for this metal–linker combination. Formation of a MnMOF-1 structure with shorter linkers is thwarted by steric clashes that preclude the formation of the Mn3 cluster. This observation prompted the use of density functional theory (DFT) simulations that showed the target material to be very dense, highly strained and thereby energetically unfavourable, but potentially, a hypothetical MnMOF-1 structure with a longer phenylethynyl spacer would be energetically feasible. Finally, the predominance of 2D MOFs formed with shorter flexible links encouraged us to use tetratopic hinged linkers to form 3D frameworks, which was vindicated by the successful synthesis of two new porous 3D Mn-based MOFs, MnMOF-L4 and MnMOF-L5. These results highlight that reticular synthesis of MOFs formed with flexible, non-linear linkers is challenging.

U2 - 10.1039/D3CE00881A

DO - 10.1039/D3CE00881A

M3 - Article

SN - 1466-8033

VL - 25

SP - 6539

EP - 6548

JO - CrystEngComm

JF - CrystEngComm

IS - 47

ER -

Understanding the structural landscape of Mn-based MOFs formed with hinged pyrazole carboxylate linkers

Abstract

Bibliographical note

Access to Document

Fingerprint

Projects

Complex-bearing Metal-Organic Frameworks: Snapshots of Reactions

Cite this