Journal
IUCRJ
Volume 5, Issue -, Pages 182-189Publisher
INT UNION CRYSTALLOGRAPHY
DOI: 10.1107/S2052252518001379
Keywords
cycloaddition reactions; supra-molecular isomerism; metal-organic frameworks; MOFs; coordination polymers; single-crystal-to-single-crystal transformations; crystal engineering; crystallization and crystal growth; solid-state transformations; structural isomerism
Funding
- Ministry of Education - Singapore (National University of Singapore Tier 1 grant) [R-143-000-678-114]
- National Research Foundation of Korea (NRF) [2016R1A2A2A05918799, 2017R1A4A1014595]
- National Research Foundation of Korea [2017R1A4A1014595, 21A20151513130, 2016R1A2A2A05918799] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
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The existence of isomerism in coordination polymeric structures offers opportunities to understand structure-function relationships. Herein the serendipitous isolation is reported of two isomeric double-pillared-layer coordination polymeric structures arising from two different types of carboxylate bonding of benzene-1,4-dicarboxylate ligands to zinc(II), which constitutes a new type of structural isomerism. The different bonding modes not only alter the shape and size of the pores, but also the nature of interpenetration and photoreactivity. Although two trans, cis, trans-bpeb ligands with conjugated olefin bonds are aligned in close proximity in both of the structures, one isomer undergoes a double [2 + 2] cycloaddition reaction and the second isomer only offers an incomplete single cycloaddition product. This work demonstrates how small changes in the structural connectivity can have an impact on the overall structural, physical and chemical properties of such materials.
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