Pseudo-5-Fold-Symmetrical Ligand Drives Geometric Frustration in Porous Metal-Organic and Hydrogen-Bonded Frameworks

Frederik Haase; Gavin A. Craig; Mickaële Bonneau; Kunihisa Sugimoto; Shuhei Furukawa

doi:10.1021/jacs.0c04450

Pseudo-5-Fold-Symmetrical Ligand Drives Geometric Frustration in Porous Metal-Organic and Hydrogen-Bonded Frameworks

Frederik Haase^*, Gavin A. Craig, Mickaële Bonneau, Kunihisa Sugimoto, Shuhei Furukawa^*

^*Corresponding author for this work

Chemistry

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

20 Scopus citations

Abstract

Reticular framework materials thrive on designability, but unexpected reaction outcomes are crucial in exploring new structures and functionalities. By combining "incompatible"building blocks, we employed geometric frustration in reticular materials leading to emergent structural features. The combination of a pseudo-C5-symmetrical organic building unit based on a pyrrole core with a C4-symmetrical copper paddlewheel synthon led to three distinct frameworks by tuning the synthetic conditions. The frameworks show structural features typical for geometric frustration: self-limiting assembly, internally stressed equilibrium structures, and topological defects in the equilibrium structure, which manifested in formation of a hydrogen-bonded framework, distorted and broken secondary building units, and dangling functional groups, respectively. The influence of geometric frustration on the CO2 sorption behavior and the discovery of a new secondary building unit shows geometric frustration can serve as a strategy to obtain highly complex porous frameworks.

Original language	English (US)
Pages (from-to)	13839-13845
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	142
Issue number	32
DOIs	https://doi.org/10.1021/jacs.0c04450
State	Published - Aug 12 2020

Bibliographical note

Funding Information:
F.H. is grateful to the Japan Society for the Promotion of Science (JSPS) for Post-Doctoral Fellowships. The authors acknowledge the iCeMS Analysis Center for access to analytical facilities. The authors also acknowledge the anonymous reviewer's detailed suggestion for the discussion of nets.

Publisher Copyright:
Copyright © 2020 American Chemical Society.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.0c04450

Cite this

@article{bed0dc9c33024b95912251ac8794e392,

title = "Pseudo-5-Fold-Symmetrical Ligand Drives Geometric Frustration in Porous Metal-Organic and Hydrogen-Bonded Frameworks",

abstract = "Reticular framework materials thrive on designability, but unexpected reaction outcomes are crucial in exploring new structures and functionalities. By combining {"}incompatible{"}building blocks, we employed geometric frustration in reticular materials leading to emergent structural features. The combination of a pseudo-C5-symmetrical organic building unit based on a pyrrole core with a C4-symmetrical copper paddlewheel synthon led to three distinct frameworks by tuning the synthetic conditions. The frameworks show structural features typical for geometric frustration: self-limiting assembly, internally stressed equilibrium structures, and topological defects in the equilibrium structure, which manifested in formation of a hydrogen-bonded framework, distorted and broken secondary building units, and dangling functional groups, respectively. The influence of geometric frustration on the CO2 sorption behavior and the discovery of a new secondary building unit shows geometric frustration can serve as a strategy to obtain highly complex porous frameworks.",

author = "Frederik Haase and Craig, {Gavin A.} and Micka{\"e}le Bonneau and Kunihisa Sugimoto and Shuhei Furukawa",

note = "Funding Information: F.H. is grateful to the Japan Society for the Promotion of Science (JSPS) for Post-Doctoral Fellowships. The authors acknowledge the iCeMS Analysis Center for access to analytical facilities. The authors also acknowledge the anonymous reviewer's detailed suggestion for the discussion of nets. Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = aug,

day = "12",

doi = "10.1021/jacs.0c04450",

language = "English (US)",

volume = "142",

pages = "13839--13845",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "32",

}

TY - JOUR

T1 - Pseudo-5-Fold-Symmetrical Ligand Drives Geometric Frustration in Porous Metal-Organic and Hydrogen-Bonded Frameworks

AU - Haase, Frederik

AU - Craig, Gavin A.

AU - Bonneau, Mickaële

AU - Sugimoto, Kunihisa

AU - Furukawa, Shuhei

N1 - Funding Information: F.H. is grateful to the Japan Society for the Promotion of Science (JSPS) for Post-Doctoral Fellowships. The authors acknowledge the iCeMS Analysis Center for access to analytical facilities. The authors also acknowledge the anonymous reviewer's detailed suggestion for the discussion of nets. Publisher Copyright: Copyright © 2020 American Chemical Society.

PY - 2020/8/12

Y1 - 2020/8/12

N2 - Reticular framework materials thrive on designability, but unexpected reaction outcomes are crucial in exploring new structures and functionalities. By combining "incompatible"building blocks, we employed geometric frustration in reticular materials leading to emergent structural features. The combination of a pseudo-C5-symmetrical organic building unit based on a pyrrole core with a C4-symmetrical copper paddlewheel synthon led to three distinct frameworks by tuning the synthetic conditions. The frameworks show structural features typical for geometric frustration: self-limiting assembly, internally stressed equilibrium structures, and topological defects in the equilibrium structure, which manifested in formation of a hydrogen-bonded framework, distorted and broken secondary building units, and dangling functional groups, respectively. The influence of geometric frustration on the CO2 sorption behavior and the discovery of a new secondary building unit shows geometric frustration can serve as a strategy to obtain highly complex porous frameworks.

AB - Reticular framework materials thrive on designability, but unexpected reaction outcomes are crucial in exploring new structures and functionalities. By combining "incompatible"building blocks, we employed geometric frustration in reticular materials leading to emergent structural features. The combination of a pseudo-C5-symmetrical organic building unit based on a pyrrole core with a C4-symmetrical copper paddlewheel synthon led to three distinct frameworks by tuning the synthetic conditions. The frameworks show structural features typical for geometric frustration: self-limiting assembly, internally stressed equilibrium structures, and topological defects in the equilibrium structure, which manifested in formation of a hydrogen-bonded framework, distorted and broken secondary building units, and dangling functional groups, respectively. The influence of geometric frustration on the CO2 sorption behavior and the discovery of a new secondary building unit shows geometric frustration can serve as a strategy to obtain highly complex porous frameworks.

UR - http://www.scopus.com/inward/record.url?scp=85089618071&partnerID=8YFLogxK

U2 - 10.1021/jacs.0c04450

DO - 10.1021/jacs.0c04450

M3 - Article

C2 - 32668902

AN - SCOPUS:85089618071

SN - 0002-7863

VL - 142

SP - 13839

EP - 13845

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 32

ER -

Pseudo-5-Fold-Symmetrical Ligand Drives Geometric Frustration in Porous Metal-Organic and Hydrogen-Bonded Frameworks

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this