期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 58, 期 42, 页码 14860-14864出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201904834
关键词
[2+2] cycloaddition; crystal engineering; metal-organic frameworks; molecular patterning; strained molecules
资金
- Ministry of Education, Singapore (National University of Singapore) [R-143-000-A12-114]
- National Research Foundation (NRF) of South Korea [2017R1A4A1014595, 2019R1A2C1002075]
- Overseas Postdoctoral Fellowship of Foresting Next-Generation Research Program through the NRF [2017R1A6A3A03006579]
- Korean government (MSICT)
- POSTEC
- National Research Foundation of Korea [2017R1A4A1014595, 2019R1A2C1002075, 2017R1A6A3A03006579] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
Conventional chemical patterning involves films of polymeric materials. Herein, we demonstrate that the presence or absence of guest solvents in the crystal voids modulates the patterning of the cyclobutane rings in highly strained metal-organic frameworks (MOFs) under UV light. The olefin pairs of the spacer ligands, which resemble a ladder-like structure, in the MOF, undergo a [2+2] cycloaddition reaction in a single-crystal-to-single-crystal manner. For instance, a partial photoreaction in the MOFs in the absence of a guest solvent as well as with dimethylacetamide in the voids generated two different patterns of the cyclobutane rings. Surprisingly, the MOF with the lattice dimethylformamide undergoes 100 % photoreaction, but the photoproduct contains broken chains. Such chemical patterning at the molecular level represents a next step in crystal engineering.
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