Supramolecular Branching and Crosslinking of Terpyridine‐Modified Copolymers: Complexation and Decomplexation Studies in Diluted Solution

Hofmeier, H Harald; Schubert, Ulrich S.

doi:10.1002/macp.200350003

Cited by 92 publications

(68 citation statements)

References 37 publications

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“…35,50,51 In this study, the reversible complexation/ decomplexation of the membranes with cobalt(II) and iron(II) was observed by the colour switch upon treatment with HEEDTA (Fig. 2C).…”

Section: Characterization and Redox Switch Behaviour Of Apcns Modiedsupporting

confidence: 51%

2,2′:6′,2′′-Terpyridine-functionalized redox-responsive hydrogels as a platform for multi responsive amphiphilic polymer membranes

et al. 2016

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a Nanophase-separated amphiphilic polymer co-networks are ideally suited as responsive membranes due to their stable co-continuous structure. Their functionalization with redox-responsive 2,2 0 :6 0 ,2 00 -terpyridine-metal complexes and light-responsive spiropyran derivatives leads to a novel material with tunable optical, redox and permeability properties. The versatility of the system in complexing various metal ions, such as cobalt or iron at different concentrations, results in a perfect monitoring over the degree of crosslinking of the hydrophilic poly(2-hydroxyethyl acrylate) channels. The reversibility of the complexation, the redox state of the metal and the isomerization to the merocyanine form upon UV illumination was evidenced by cyclic voltammetry, UV-Vis and permeability measurements under sequential conditions. Thus, the membrane provides light and redox addressable functionalities due to its adjustable and mechanically stable hydrogel network.

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“…35,50,51 In this study, the reversible complexation/ decomplexation of the membranes with cobalt(II) and iron(II) was observed by the colour switch upon treatment with HEEDTA (Fig. 2C).…”

Section: Characterization and Redox Switch Behaviour Of Apcns Modiedsupporting

confidence: 51%

2,2′:6′,2′′-Terpyridine-functionalized redox-responsive hydrogels as a platform for multi responsive amphiphilic polymer membranes

et al. 2016

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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.…”

mentioning

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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“…[3][4][5][6][7][8][9][10][11][12][13] 2,2Ј:6Ј,2ЈЈ-Terpyridines bearing well-defined π-conjugated substituents at the 4Ј-position are known to exhibit attractive electronic and optical properties. [6,8,10,[14][15][16][17][18][19][20][21][22][23][24][25] When two 2,2Ј:6Ј,2ЈЈ-terpyridine units are introduced at either end of a rigid conjugated spacer, the resulting ditopic bis(terpyridine) ligand enables the synthesis of metallo-supramolecular polymers by coordination with different metal ions. Several publications dealing with the synthesis and characterization of such conjugated terpyrid-ine derivatives were fully characterized by 1 H and 13 C NMR spectroscopy, UV/Vis absorption and emission measurements as well as MALDI-TOF MS.…”

Section: Introductionmentioning

confidence: 99%

π‐Conjugated 2,2′:6′,2″‐Bis(terpyridines): Systematical Tuning of the Optical Properties by Variation of the Linkage between the Terpyridines and the π‐Conjugated System

et al. 2010

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Abstract2,2′:6′,2″‐Terpyridines bearing well‐defined π‐conjugated substituents at the 4′‐position are known to exhibit interesting electronic and optical properties. The systematic variation of both the spacer unit and the linker in conjugated bis(terpyridines) has resulted in a library of π‐conjugated systems, enabling the study of the structure–property relationships of these materials. We have proven the Huisgen 1,3‐dipolar cycloaddition reaction to be a versatile tool for connecting conjugated systems, even though the conjugation is hindered by the introduced triazole moiety. All the terpyridine derivatives were fully characterized by 1H and 13C NMR spectroscopy, UV/Vis absorption and emission measurements as well as MALDI‐TOF MS. Thin films of the materials were produced by spin‐coating and subsequently characterized. Because tuning of the band gap of the materials over a wide range is possible, quantum yields of up to 85 % and extinction coefficients of around 100000 M–1 cm–1 could be observed, the compounds might be promising candidates for the design of new functional supramolecular materials.

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Supramolecular Branching and Crosslinking of Terpyridine‐Modified Copolymers: Complexation and Decomplexation Studies in Diluted Solution

Cited by 92 publications

References 37 publications

2,2′:6′,2′′-Terpyridine-functionalized redox-responsive hydrogels as a platform for multi responsive amphiphilic polymer membranes

2,2′:6′,2′′-Terpyridine-functionalized redox-responsive hydrogels as a platform for multi responsive amphiphilic polymer membranes

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

π‐Conjugated 2,2′:6′,2″‐Bis(terpyridines): Systematical Tuning of the Optical Properties by Variation of the Linkage between the Terpyridines and the π‐Conjugated System

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