Polymer Synthesis in Coordination Nanospaces

Abstract

In nature, biopolymers are efficiently synthesized by multilevel arrangements of monomers within constrained molecular-level spaces. These biological systems produce regio-and stereoregular polymers with uniform molecular weights, and can also arrange the higher order structures of the resulting polymers. Inspired by the elegant operations of polymerization in biological systems, polymer synthesis in artificial confined geometries is a promising strategy for the control of polymer primary structures and the design of well-defined nanostructures. Recently, we have established a new methodology for controlling polymer synthesis using microporous coordination compounds. In this account, recent progress and future perspectives of polymerizations in these coordination nanospaces are reviewed.

Metal–organic framework composites

“…The recovered PSt showed much narrower molecular weight distribution than those synthesized in bulk and solution. In the subsequent studies, the efforts in radical polymerization were further directed to controlling the molecular weight, 234 tacticity, 235,236 dimensions, 231,237 and copolymer sequence 238 of the resulting polymers, which have been extensively summarized in several reviews 57,239,240 and will not be discussed herein in detail. Besides, our group has reported the This journal is © The Royal Society of Chemistry 2014 polymerization of furfuryl alcohol (FA) in MOFs and the carbonization of the resultant PFA@MOF composites for porous carbon preparation.…”

Radicals in metal–organic frameworks

“…6 More recently attention has been drawn towards the possibility of developing more advanced properties such as magnetism, spin-state bistability, electron, hole and ion mobility, ferroelectricity, luminescence, redox and non-linear optical activity. These attributes give rise to myriad applications, not limited to but including: chemical sensing, 7 small molecule sequestration (e.g., CO 2 ) 8 and release (e.g., drugs), 9 electronic devices, 10 magnetic refrigeration, 11 second harmonic generation, 12 structural determination, 13 polymer templating, 14 as well as multiple platforms for clean energy. 15 Furthermore, the possibility of combining these elements giving rise to multifunctionality is highly sought aer and difficult to induce in traditional porous materials such as zeolites.…”

An Experimental Study on the Processes of Hierarchical Morphology Replication by Means of a Mesocrystal: A Case Study of Poly(3,4-ethylenedioxythiophene)

“…A variety of templates have been developed for morphology replications. Biological architectures with complex shapes were used as templates for morphogenesis. − Porous materials with the controlled pore space in nanometer scale, such as mesoporous materials and porous coordination polymers, served as templates for generation of low-dimensional nanostructures through the replication. − Self-assembled molecules were designed as templates for generation of nanostructures. , However, it is not so easy to replicate the morphologies from nanometer to millimeter scales by using typical templates. A general approach for the hierarchical morphology replication is required.…”