Adaptive Discovery of Uncharted Zeolitic Imidazolate Frameworks
4 affiliations
- 1Department of Chemistry
- 2California
- 3Departments of Chemistry and Chemical Engineering, and AIMATRY
- 4Tsinghua University
Abstract
Discovering new zeolitic imidazolate framework (ZIF) structures remains a major challenge because their assembly depends on the nature of the linker and synthesis conditions. Here, we introduce linker width as a design parameter for ZIF synthesis. We designed 4-substituted benzimidazole linkers with expanded width and combined them with smaller linkers in an adaptive machine-learning (ML) high-throughput strategy. This adaptive discovery scheme yielded nine new mixed-linker ZIFs, including six adopting the previously unrealized bcv topology. Single-crystal structural analysis reveals ordered linker distributions in which the wider 4-substituted benzimidazolate linkers code for the formation of 10-membered-ring needed for the apertures of the bcv cage. Comparison with representative mixed-linker ZIFs further identifies the width of linkers and the extension ratio as steric descriptors of topology selection. These results establish chemically interpretable design principles for mixed-linker ZIF assembly and demonstrate how linker design coupled with ML-guided synthesis can access unexplored regions of chemical space.
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BibTeX
@misc{lin2026adaptive,
title = {{Adaptive Discovery of Uncharted Zeolitic Imidazolate Frameworks}},
author = {Yen-hsu Lin and Zichao Rong and Mei-Yan Gao and Sara Alnasser and Omar M. Yaghi},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008404/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008404/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Adaptive Discovery of Uncharted Zeolitic Imidazolate Frameworks
AU - Yen-hsu Lin
AU - Zichao Rong
AU - Mei-Yan Gao
AU - Sara Alnasser
AU - Omar M. Yaghi
PY - 2026
DA - 2026/09/07
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008404/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008404/v1
AB - Discovering new zeolitic imidazolate framework (ZIF) structures remains a major challenge because their assembly depends on the nature of the linker and synthesis conditions. Here, we introduce linker width as a design parameter for ZIF synthesis. We designed 4-substituted benzimidazole linkers with expanded width and combined them with smaller linkers in an adaptive machine-learning (ML) high-throughput strategy. This adaptive discovery scheme yielded nine new mixed-linker ZIFs, including six adopting the previously unrealized bcv topology. Single-crystal structural analysis reveals ordered linker distributions in which the wider 4-substituted benzimidazolate linkers code for the formation of 10-membered-ring needed for the apertures of the bcv cage. Comparison with representative mixed-linker ZIFs further identifies the width of linkers and the extension ratio as steric descriptors of topology selection. These results establish chemically interpretable design principles for mixed-linker ZIF assembly and demonstrate how linker design coupled with ML-guided synthesis can access unexplored regions of chemical space.
ER -