Water‐Soluble Building Blocks for Terpyridine‐Containing Supramolecular Polymers: Synthesis, Complexation, and pH Stability Studies of Poly(ethylene oxide) Moieties

Lohmeijer, Bgg Bas; Schubert, Ulrich S.

doi:10.1002/macp.200390078

Cited by 95 publications

(80 citation statements)

References 26 publications

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“…Looking at AA homopolymer systems, this concept was recently realized using poly(ethylene oxide) functionalized with one terpyridine, which, upon complexation with various transition metal ions, gave water-soluble polymers with double the mass of the starting polymer ligand plus the metal and counter ions. [33] These complexes were investigated with respect to their pH sensitivity. It was found that the iron(II)-, cobalt(II)-, zinc(II)-, and cadmium(II)-containing polymers showed decomplexation at high and low pH (13 and 1, respectively).…”

Section: Polydisperse Systems Containing 22¢:6¢2²-terpyridine Metalmentioning

confidence: 99%

New Functional Polymers and Materials Based on 2,2′:6′,2″‐Terpyridine Metal Complexes

2004

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New inorganic–organic hybrid structures based on metal complexes have become of increasing interest over the last few decades in the search for new materials. Many different polypyridyl metal complexes have been investigated. Recently, a strong increase in interest regarding 2,2′:6′,2″‐terpyridine has been observed. In particular, octahedral bis‐2,2′:6′,2″‐terpyridine metal complexes offer the advantages of increased symmetry and, in the case of ruthenium(III)/ruthenium(II) complexation, an entrance to a directed complexation technique. Apart from the combination with polymeric systems, ordered inorganic–organic structures on surfaces are becoming better understood concurrently with the development of sophisticated nanotechnology characterization techniques. There are many ongoing efforts that include terpyridine complex structures, especially concerning photophysical processes such as solar light to energy conversion. This review deals with the incorporation of terpyridine complexes into polymeric structures such as poly(ethylene glycol), poly(styrene), dendrimers, biomacromolecules, micelles, and resins, as well as the combination of terpyridine complexes with surfaces for electrocatalytic, photophysical, and self‐assembly purposes.

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Section: Polydisperse Systems Containing 22¢:6¢2²-terpyridine Metalmentioning

confidence: 99%

New Functional Polymers and Materials Based on 2,2′:6′,2″‐Terpyridine Metal Complexes

2004

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“…Various investigations of the complexation and decomplexation behavior of MA C H T U N G T R E N N U N G (tpy) 2 architectures have been reported. Either metal-complexing ligands such as hydroxyethylethylenediaminetriacetic acid (HEEDTA) [32] or variations of the pH value [33][34] can be used in most cases to cleave the coordinative bonds in tpy complexes. We found that in the case of Fe (7) 2 2 + , addition of one equivalent of 1,8-diazabicycloA C H T U N G T R E N N U N G [5.4.0]undec-7-ene (DBU) in chloroform is sufficient for complete decomplexation within 12 h at room temperature.…”

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confidence: 99%

Self‐Assembly of Supramolecular Architectures and Polymers by Orthogonal Metal Complexation and Hydrogen‐Bonding Motifs

Grimm

Ulm

Gröhn

et al. 2011

Chemistry A European J

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A modular construction kit with two orthogonal noncovalent binding sites for self-assembly of supramolecular architectures is presented. The heteroditopic building blocks contain a terpyridine (tpy) unit for coordination of metal ions and a Hamilton receptor for multiple H-bonding of cyanuric acid derivatives. The association constants of ligand binding of M(II) complexes (M=Ru, Zn, Fe, and Pt) with a dendritic end cap were determined to be in the range of 10(2) and 10(4) L mol(-1) in chloroform. The capabilities for binding of metal ions were investigated by (1)H NMR and UV/Vis spectroscopy. The Fe complexes are most appropriate for the generation of discrete and high-ordered architectures due to their strong tendency to form FeL(2) complexes. Superstructures are readily formed in a one-pot procedure at room temperature. No mutual interactions between the orthogonal binding motifs were observed, and this demonstrates the highly specific nature of each binding process. Decomplexation experiments were carried out to examine the reversibility of Fe-tpy coordination. Substitution of the terminal end cap with a homoditopic bis-cyanurate linkage leads to formation of an iron-containing supramolecular strand. Formation of coordination polymers was confirmed by viscosity measurements. The supramolecular polymer strands can be reversibly cleaved by addition of a terminating cyanuric acid building block, and this proves the dynamic nature of this noncovalent polymerization process.

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“…[21] The product was characterized by different techniques including 1 the complexation of the functionalized terpyridine ligand 3 with three different metal ions in low oxidation states: Ni 2þ , Fe 2þ , and Co 2þ . [22] The selection of the transition metal ions was done in agreement with their relatively high-binding strength known from previous studies, [11,12] in order to study the differences which could result in the stability of the pure prepared metal-bis(terpyridine)-poly(ethylene glycol) model complexes in solution during the SEC measurements.…”

Section: Resultsmentioning

confidence: 99%

“…IR spectra of the metallosupramolecular polymers are similar to the model complexes described earlier. [22] For the case of 6, the UV-Vis spectrum revealed an intense absorption in the visible region, the color of the complex being intense purple. A distinct metal-to-ligand charge transfer (MLCT) band was detected at 556 nm.…”

Section: Resultsmentioning

confidence: 99%

New Insights into Nickel(II), Iron(II), and Cobalt(II) Bis‐Complex‐Based Metallo‐Supramolecular Polymers

Chiper

Meier

Kranenburg

et al. 2007

Macro Chemistry & Physics

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One of the most important characterization methods for macromolecules is SEC. The main difficulty for this type of measurements concerning metallo‐supramolecular polymers based on terpyridines is related to the interaction between the charged supramolecular species and the SEC column material. In this paper, we report new studies on the characterization and the stability of supramolecular polymers based on terpyridine metal complexes utilizing SEC. The main aspects concerning the equilibrium between complexed and uncomplexed species are discussed in detail. The present study reveals a strong relationship between the binding strength of the metal ion used and the stability of the terpyridine metal complex during the SEC measurements, which is in agreement with previously published results regarding the stability of small terpyridine metal complexes in solution. These results can lead to improved analytic possibilities and to a better fundamental understanding of the mentioned metallo‐supramolecular polymers. Furthermore, the prepared chain‐extended supramolecular‐polymer was analyzed by depth‐sensing indentation proving an increase in elastic modulus in comparison with the starting material.magnified image

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Water‐Soluble Building Blocks for Terpyridine‐Containing Supramolecular Polymers: Synthesis, Complexation, and pH Stability Studies of Poly(ethylene oxide) Moieties

Cited by 95 publications

References 26 publications

New Functional Polymers and Materials Based on 2,2′:6′,2″‐Terpyridine Metal Complexes

New Functional Polymers and Materials Based on 2,2′:6′,2″‐Terpyridine Metal Complexes

Self‐Assembly of Supramolecular Architectures and Polymers by Orthogonal Metal Complexation and Hydrogen‐Bonding Motifs

New Insights into Nickel(II), Iron(II), and Cobalt(II) Bis‐Complex‐Based Metallo‐Supramolecular Polymers

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