Metallo-Network Polymers: Reversible CO Binding to an Immobilized Copper(I) Complex

Abstract

Copolymerization of molecular assemblies into organic hosts is an effective way of fabricating new materials having desirable chemical or physical properties. The assembly of the molecular species prior to polymerization is advantageous because of the greater control of the structure and amount of species incorporated into the polymer and the possibility of regulating their microenvironments. Recent examples of this method in the synthesis of new polymers include the monodispersal of metallic nanoclusters into organic polymer hosts' and molecular imprinting of selective binding sites into highly cross-linked network polymers.2 We describe herein an application of this copolymerization approach for designing metal ion sites in network polymers.3•4Our objective is to use the copolymerization process to synthesize sites in the polymer that can bind metal ions or stabilize metal-small molecule adducts. The macroporous character of these polymers should allow the incorporated metal ion to bind additional ligands not present during polymerization.

Metal ion coordination interactions for biomolecule recognition: a review

“…After polymerization the template molecule is removed with appropriate agents. In order to use the material with other metal ions, it can be washed with complexing agents such as ethylenediaminetetraacetic acid (EDTA) to remove all the metal content then the other metal ion can be reloaded [14].…”

Preparation and Catalytic Performances of a Molecularly Imprinted Ru‐Complex Catalyst with an NH2 Binding Site on a SiO2 Surface

“…[57][58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73][74] Mosbach reported Co-containing polymers imprinted with the shape of an aldolase, which is regarded as a transition-state analogue of aldol condensation. [60] Severin prepared molecularly imprinted polymers with Ru and Rh complexes using a template with a similar shape to a transition state of the transfer hydrogenation of prochiral ketones.…”

“…For the regulation of shape-selective catalysis, a molecularly imprinted cavity should be prepared close to a catalytically active site to facilitate molecular imprinting of the metal complex of which a ligand is utilized as a template. [57][58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73][74] Further developments of molecularly imprinted catalysts have also been reported: acid or base catalysts with molecularly imprinted cavities were prepared, such as footprint catalysts, [46][47][48] phosphonate-imprinted SiO 2 , [49] SiO 2 …”

Designing selective sites in templated polymers utilizing coordinative bonds

“…However, high efficiency with nearly all templates producing functional binding sites, and reasonable solubility of the templated material in common organic solvents as well as enabled separation of imperfectly assembled binding sites reimburse for the synthetic efforts making this approach very promising for future developments of templated polymers. Taking advantage of the established rebinding properties achieved for carbon monoxide [19] and oxygen [20] due to site isolation of immobilized metal complexes in macroporous polymers [101], a polymer for reversible binding of the biologically important nitrogen oxide, NO, was prepared under similar conditions applying 4-dimethylaminopyridine, dmap, as template and a cobalt(III) complex of bis[2-hydroxy-4-(4-vinylbenzylmethoxy)benzaldehyde]ethylenediimine (19) as functional monomer (Scheme 9) [102].…”

“…Instead CO binding is permitted after removal of Ag(I) ions and occupation of the metal site with Cu(I) ions (Scheme 1) [19].…”