Formation of a Syndiotactic Organic Polymer Inside a MOF by a [2+2] Photo‐Polymerization Reaction |
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Authors: | Dr. In‐Hyeok Park Dr. Raghavender Medishetty Hyeong‐Hwan Lee Caroline Evania Mulijanto Hong Sheng Quah Prof. Shim Sung Lee Prof. Jagadese J. Vittal |
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Affiliation: | 1. Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju 660‐701 (Republic of Korea);2. Department of Chemistry, National University of Singapore, 3, Science Drive 3, Singapore 117543 (Singapore) |
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Abstract: | Getting suitable crystals for single‐crystal X‐ray crystallographic analysis still remains an art. Obtaining single crystals of metal–organic frameworks (MOFs) containing organic polymers poses even greater challenges. Here we demonstrate the formation of a syndiotactic organic polymer ligand inside a MOF by quantitative [2+2] photopolymerization reaction in a single‐crystal‐to‐single‐crystal manner. The spacer ligands with trans,trans,trans‐conformation in the pillared‐layer MOF with guest water molecules in the channels, undergo pedal motion to trans,cis,trans‐conformation prior to [2+2] photo‐cycloaddition reaction and yield single crystals of MOF containing two‐dimensional coordination polymers fused with the organic polymer ligands. We also show that the organic polymer in the single crystals can be depolymerized reversibly by cleaving the cyclobutane rings upon heating. These MOFs also show interesting photoluminescent properties and sensing of small organic molecules. |
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Keywords: | [2+2] cycloaddition metal– organic frameworks pedal motion sensors syndiotactic polymers |
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