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Formation of a Syndiotactic Organic Polymer Inside a MOF by a [2+2] Photo‐Polymerization Reaction
Author(s) -
Park InHyeok,
Medishetty Raghavender,
Lee HyeongHwan,
Mulijanto Caroline Evania,
Quah Hong Sheng,
Lee Shim Sung,
Vittal Jagadese J.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201502179
Subject(s) - cyclobutane , polymer , polymerization , tacticity , metal organic framework , molecule , ligand (biochemistry) , materials science , coordination polymer , single crystal , photopolymer , photochemistry , crystallography , polymer chemistry , chemistry , organic chemistry , ring (chemistry) , biochemistry , receptor , adsorption , composite material
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.