Formation of a Syndiotactic Organic Polymer Inside a MOF by a [2+2] Photo-Polymerization Reaction

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...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie (International ed.) 2015-06, Vol.54 (25), p.7313-7317
Main Authors: Park, In-Hyeok, Medishetty, Raghavender, Lee, Hyeong-Hwan, Mulijanto, Caroline Evania, Quah, Hong Sheng, Lee, Shim Sung, Vittal, Jagadese J.
Format: Article
Language:English
Subjects:
[2+2] cycloaddition
Cyclobutane
Formations
Ligands
metal-organic frameworks
pedal motion
Pedals
Photoluminescence
sensors
Single crystals
Spacers
syndiotactic polymers
Syndiotacticity
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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. Pedaling for cylobutane polymers: A syndiotactic polymer ligand embedded inside a metal–organic framework (MOF) was formed through pedal motions of spacer ligands before undergoing a [2+2] cycloaddition reaction in the solid state.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201502179