Structural Characterization of Pristine and Defective [Zr12(μ3-O)8(μ3-OH)8(μ2-OH)6]18+ Double-Node Metal-Organic Framework and Predicted Applications for Single-Site Catalytic Hydrolysis of Sarin

Mohammad R. Momeni; Chris Cramer

doi:10.1021/acs.chemmater.8b01913

Structural Characterization of Pristine and Defective [Zr₁₂(μ₃-O)₈(μ₃-OH)₈(μ₂-OH)₆]¹⁸⁺ Double-Node Metal-Organic Framework and Predicted Applications for Single-Site Catalytic Hydrolysis of Sarin

Mohammad R. Momeni, Chris Cramer

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

40 Scopus citations

Abstract

Periodic PBE-D3 and M06-L calculations predict the lowest-energy proton topology of a [Zr₆(μ₃-O)₄(μ₃-OH)₄(μ₂-OH)₃]₂ Zr^IV-MOF (J. Am. Chem. Soc. 2017, 139, 7004-7011), which has a unique double-node structure, to be 73.4 and 64.2 kcal/mol more stable than that originally proposed. Mono- and bidefective Zr₁₂ secondary building units derived from this topology and built by removing one and two bridging terphenyldicarboxylate linkers and saturating the remaining open Zr^IV metal sites with hydroxyl and aqua groups, are predicted to exhibit higher reactivity for the hydrolysis of sarin nerve agent than other coordinatively unsaturated Zr₆-based MOFs reported to date.

Original language	English (US)
Pages (from-to)	4432-4439
Number of pages	8
Journal	Chemistry of Materials
Volume	30
Issue number	13
DOIs	https://doi.org/10.1021/acs.chemmater.8b01913
State	Published - Jul 10 2018

Bibliographical note

Funding Information:
This work was supported as part of the Nanoporous Materials Genome Center, funded by the U.S. DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (Award DE-FG02-17ER16362). The authors acknowledge the Minnesota Supercomputing Institute (MSI) for providing resources that contributed to the research results reported within this paper. M.R.M. is grateful for helpful discussions with Manuel Ortuño, Omar Farha, and Timur Islamoglu.

Funding Information:
This work was supported as part of the Nanoporous Materials Genome Center, funded by the U.S. DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (Award DE-FG02-17ER16362).

Publisher Copyright:
© 2018 American Chemical Society.

Publisher link

10.1021/acs.chemmater.8b01913

Find It

Find It at U of M Libraries

Cite this

Structural Characterization of Pristine and Defective [Zr₁₂(μ₃-O)₈(μ₃-OH)₈(μ₂-OH)₆]¹⁸⁺ Double-Node Metal-Organic Framework and Predicted Applications for Single-Site Catalytic Hydrolysis of Sarin. / Momeni, Mohammad R.; Cramer, Chris.
In: Chemistry of Materials, Vol. 30, No. 13, 10.07.2018, p. 4432-4439.

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

@article{11968213234f4ac2b89da3de1455a662,

title = "Structural Characterization of Pristine and Defective [Zr12(μ3-O)8(μ3-OH)8(μ2-OH)6]18+ Double-Node Metal-Organic Framework and Predicted Applications for Single-Site Catalytic Hydrolysis of Sarin",

abstract = "Periodic PBE-D3 and M06-L calculations predict the lowest-energy proton topology of a [Zr6(μ3-O)4(μ3-OH)4(μ2-OH)3]2 ZrIV-MOF (J. Am. Chem. Soc. 2017, 139, 7004-7011), which has a unique double-node structure, to be 73.4 and 64.2 kcal/mol more stable than that originally proposed. Mono- and bidefective Zr12 secondary building units derived from this topology and built by removing one and two bridging terphenyldicarboxylate linkers and saturating the remaining open ZrIV metal sites with hydroxyl and aqua groups, are predicted to exhibit higher reactivity for the hydrolysis of sarin nerve agent than other coordinatively unsaturated Zr6-based MOFs reported to date.",

author = "Momeni, {Mohammad R.} and Chris Cramer",

note = "Funding Information: This work was supported as part of the Nanoporous Materials Genome Center, funded by the U.S. DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (Award DE-FG02-17ER16362). The authors acknowledge the Minnesota Supercomputing Institute (MSI) for providing resources that contributed to the research results reported within this paper. M.R.M. is grateful for helpful discussions with Manuel Ortu{\~n}o, Omar Farha, and Timur Islamoglu. Funding Information: This work was supported as part of the Nanoporous Materials Genome Center, funded by the U.S. DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (Award DE-FG02-17ER16362). Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = jul,

day = "10",

doi = "10.1021/acs.chemmater.8b01913",

language = "English (US)",

volume = "30",

pages = "4432--4439",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

number = "13",

}

TY - JOUR

T1 - Structural Characterization of Pristine and Defective [Zr12(μ3-O)8(μ3-OH)8(μ2-OH)6]18+ Double-Node Metal-Organic Framework and Predicted Applications for Single-Site Catalytic Hydrolysis of Sarin

AU - Momeni, Mohammad R.

AU - Cramer, Chris

N1 - Funding Information: This work was supported as part of the Nanoporous Materials Genome Center, funded by the U.S. DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (Award DE-FG02-17ER16362). The authors acknowledge the Minnesota Supercomputing Institute (MSI) for providing resources that contributed to the research results reported within this paper. M.R.M. is grateful for helpful discussions with Manuel Ortuño, Omar Farha, and Timur Islamoglu. Funding Information: This work was supported as part of the Nanoporous Materials Genome Center, funded by the U.S. DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences (Award DE-FG02-17ER16362). Publisher Copyright: © 2018 American Chemical Society.

PY - 2018/7/10

Y1 - 2018/7/10

N2 - Periodic PBE-D3 and M06-L calculations predict the lowest-energy proton topology of a [Zr6(μ3-O)4(μ3-OH)4(μ2-OH)3]2 ZrIV-MOF (J. Am. Chem. Soc. 2017, 139, 7004-7011), which has a unique double-node structure, to be 73.4 and 64.2 kcal/mol more stable than that originally proposed. Mono- and bidefective Zr12 secondary building units derived from this topology and built by removing one and two bridging terphenyldicarboxylate linkers and saturating the remaining open ZrIV metal sites with hydroxyl and aqua groups, are predicted to exhibit higher reactivity for the hydrolysis of sarin nerve agent than other coordinatively unsaturated Zr6-based MOFs reported to date.

AB - Periodic PBE-D3 and M06-L calculations predict the lowest-energy proton topology of a [Zr6(μ3-O)4(μ3-OH)4(μ2-OH)3]2 ZrIV-MOF (J. Am. Chem. Soc. 2017, 139, 7004-7011), which has a unique double-node structure, to be 73.4 and 64.2 kcal/mol more stable than that originally proposed. Mono- and bidefective Zr12 secondary building units derived from this topology and built by removing one and two bridging terphenyldicarboxylate linkers and saturating the remaining open ZrIV metal sites with hydroxyl and aqua groups, are predicted to exhibit higher reactivity for the hydrolysis of sarin nerve agent than other coordinatively unsaturated Zr6-based MOFs reported to date.

UR - http://www.scopus.com/inward/record.url?scp=85048713121&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85048713121&partnerID=8YFLogxK

U2 - 10.1021/acs.chemmater.8b01913

DO - 10.1021/acs.chemmater.8b01913

M3 - Article

AN - SCOPUS:85048713121

SN - 0897-4756

VL - 30

SP - 4432

EP - 4439

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 13

ER -

Structural Characterization of Pristine and Defective [Zr₁₂(μ₃-O)₈(μ₃-OH)₈(μ₂-OH)₆]¹⁸⁺ Double-Node Metal-Organic Framework and Predicted Applications for Single-Site Catalytic Hydrolysis of Sarin

Abstract

Bibliographical note

Publisher link

Find It

Other files and links

Fingerprint

NMGC: Nanoporous Materials Genome: Methods and Software to Optimize Gas Storage, Separations, and Catalysis (Phase 2)

Cite this

Structural Characterization of Pristine and Defective [Zr12(μ3-O)8(μ3-OH)8(μ2-OH)6]18+ Double-Node Metal-Organic Framework and Predicted Applications for Single-Site Catalytic Hydrolysis of Sarin

Abstract

Bibliographical note

Publisher link

Find It

Other files and links

Fingerprint

Projects

NMGC: Nanoporous Materials Genome: Methods and Software to Optimize Gas Storage, Separations, and Catalysis (Phase 2)

Cite this

Structural Characterization of Pristine and Defective [Zr₁₂(μ₃-O)₈(μ₃-OH)₈(μ₂-OH)₆]¹⁸⁺ Double-Node Metal-Organic Framework and Predicted Applications for Single-Site Catalytic Hydrolysis of Sarin