Probing ligand conformation and net dimensionality in a series of tetraphenylethene-based metal–organic frameworks

Johnson, Hannah M.; Hurlock, Matthew J.; Lare, Monipak F.; Forseth, Lauren V.; Mosset, Dylan M.; Li, Jiahong; Zhang, Qiang

doi:10.3389/fchem.2024.1396123

Title: Probing ligand conformation and net dimensionality in a series of tetraphenylethene-based metal–organic frameworks

Journal Article · 25 April 2024 · Frontiers in Chemistry

DOI: https://doi.org/10.3389/fchem.2024.1396123 · OSTI ID:2471197

Johnson, Hannah M. ^[1]; Hurlock, Matthew J. ^[2]; Lare, Monipak F. ^[1]; Forseth, Lauren V. ^[1]; Mosset, Dylan M. ^[1]; Li, Jiahong ^[1]; Zhang, Qiang ^[1]

Washington State Univ., Pullman, WA (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Tetraphenylethene-based ligands with lowered symmetry are promising building blocks for the construction of novel luminescent metal–organic frameworks (MOFs). However, few examples have been reported, and predicting the ligand conformation and the dimensionality of the resulting MOF remains challenging. In order to uncover how synthetic conditions and accessible ligand conformations may affect the resulting MOF structure, four new MOF structures were synthesized under solvothermal conditions using the meta-coordinated tetraphenylethene-based ligand m-ETTC and paddlewheel SBUs composed of Co(II), Cu(II), and Zn(II). WSU-10 (WSU = Washington State University) is formed with either Zn or Cu comprising stacked psuedo-2D layers. The dimensionality of WSU-10 can be intentionally increased through the addition of pyrazine as a pillar ligand into the synthesis, forming the 3D structure WSU-11. The third structure, WSU-20, is formed by the combination of Zn or Co with m-ETTC and is intrinsically 3D without the use of a pillar ligand; interestingly, this is the result of a distortion in the paddlewheel SBU. Finally, Cu was also found to form a new structure (WSU-12), which displays an m-ETTC conformation unique from that found in the other isolated MOFs. Structural features are compared across the series and a mechanistic relationship between WSU-10 and -20 is proposed, providing insight into the factors that can encourage the generation of frameworks with increased dimensionality.

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Research Organization:: Washington State Univ., Pullman, WA (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE)

OSTI ID:: 2471197

Journal Information:: Frontiers in Chemistry, Journal Name: Frontiers in Chemistry Vol. 12; ISSN 2296-2646

Publisher:: Frontiers Research FoundationCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ligand conformation
metal-organic framework
net dimensionality
solvent lability
tetraphenylethene

CCDC 2295734: Experimental Crystal Structure Determination M., Johnson, Hannah; J., Hurlock, Matthew; F., Lare, Monipak https://doi.org/10.5517/ccdc.csd.cc2h1wyd The current record is supplemented by this dataset	dataset	January 2024
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Title: Probing ligand conformation and net dimensionality in a series of tetraphenylethene-based metal–organic frameworks

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