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 -