Cyclobutanedicarboxylate Metal–Organic Frameworks as a Platform for Dramatic Amplification of Pore Partition Effect

Wang, Wei; Yang, Huajun; Chen, Yichong; Bu, Xianhui; Feng, Pingyun

doi:10.1021/jacs.3c05980

Cyclobutanedicarboxylate Metal–Organic Frameworks as a Platform for Dramatic Amplification of Pore Partition Effect

Journal Article · Fri Aug 04 00:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.3c05980· OSTI ID:2205465

Wang, Wei ^[1]; ^[2]; Chen, Yichong ^[3]; ^[2]; ^[3]

University of California, Riverside, CA (United States); UC Riverside
California State University, Long Beach, CA (United States)
University of California, Riverside, CA (United States)

Ultrafine tuning of MOF structures at sub-angstrom or picometer levels can help improve separation selectivity for gases with subtle differences. However, for MOFs with large-enough pore size, the effect from ultrafine tuning on sorption can be muted. Here we show an integrative strategy that couples together extreme pore compression with ultrafine pore tuning. Furthermore, this strategy is made possible by unique combination of two features of the pacs platform (pacs = partitioned acs): multi-modular framework and exceptional tolerance towards isoreticular replacement. Specifically, we use one module (Ligand 1, L1) to shrink pore size to an extreme minimum on pacs. A compression ratio of about 30% was achieved (based on unit-cell c/a ratio) from prototypical 1,4-benzenedicarboxylate-pacs to trans-1,3-cyclobutanedicarboxylate-pacs. This is followed by using another module (Ligand 2, L2) for ultrafine pore tuning (< 3% compression). This L1-L2 strategy increases C₂H₂/CO₂ selectivity from 2.6 to 20.8 and gives rise to excellent experi-mental breakthrough performance. Being the shortest cyclic dicarboxylate that mimics para-benzene-based moieties us-ing bioisosteric (BIS) strategy on pacs, trans-1,3-cyclobutanedicarboxylate-based MOF chemistry offers new opportuni-ties in MOF chemistry.

View Accepted Manuscript (DOE)

Research Organization:: University of California, Riverside, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: SC0010596

OSTI ID:: 2205465

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 32 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cyclobutanedicarboxylate Metal–Organic Frameworks as a Platform for Dramatic Amplification of Pore Partition Effect

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