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Isoreticular Crystallization of Highly Porous Cubic Covalent Organic Cage Compounds

preprint
submitted on 28.02.2021, 14:57 and posted on 03.03.2021, 04:55 by Svetlana Ivanova, Eva Köster, Julian J. Holstein, Niklas Keller, Guido H. Clever, Thomas Bein, Florian Beuerle

Modular frameworks featuring well-defined pore structures in microscale domains establish tailor-made porous materials. For open molecular solids however, maintaining long-range order after desolvation is inherently challenging, since packing is usually governed by only a few supramolecular interactions. Here we report on two series of nanocubes obtained by co-condensation of two different hexahydroxy tribenzotriquinacenes (TBTQs) and benzene-1,4-diboronic acids (BDBAs) with varying linear alkyl chains in 2,5-position. nButyl groups at the apical position of the TBTQ vertices yielded soluble model compounds, which were analyzed by mass spectrometry and NMR spectroscopy. In contrast, methyl-substituted cages spontaneously crystallized as isostructural and highly porous solids with BET surface areas and pore volumes of up to 3426 m2 g−1 and 1.82 cm3 g−1. Single crystal X-ray diffraction and sorption measurements revealed an intricate cubic arrangement of alternating micro- and mesopores in the range of 0.97–2.2 nm that are fine-tuned by the alkyl substituents at the BDBA linker.

Funding

Deutsche Forschungsgemeinschaft (BE4808/2-1)

Collaborative Research Network “Solar Technologies Go Hybrid” of the Bavarian Ministry of Science, Research and the Arts

History

Email Address of Submitting Author

florian.beuerle@uni-wuerzburg.de

Institution

University of Würzburg

Country

Germany

ORCID For Submitting Author

0000-0001-7239-8327

Declaration of Conflict of Interest

There are no conflicts to declare.

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