From terpyridine-based assemblies to metallo-supramolecular polyelectrolytes (MEPEs)

Schwarz, Guntram; Hasslauer, Iris; Kurth, Dirk G.

doi:10.1016/j.cis.2013.12.010

Cited by 36 publications

(33 citation statements)

References 122 publications

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“…1 By such a methodology many, one, two or three dimensional structures has been produced and used as smart materials for various applications. [3][4][5][6][7] As a matter of fact the three chelating pyridine groups allow the formation of octahedral metallic complexes having high binding constants and no enantiomers with many metals. Owing to the large range of available organic ligands and metallic cations, coordination polymers offer a multitude of possibilities to develop intelligent materials with tuneable properties.…”

Section: Introductionmentioning

confidence: 99%

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Alternated bimetallic [Ru–M] (M = Fe²⁺, Zn²⁺) coordination polymers based on [Ru(bpy)₃]²⁺ units connected to bis-terpyridine ligands: synthesis, electrochemistry and photophysics in solution or in thin film on electrodes

et al. 2014

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Two alternated bimetallic Ru-Fe and Ru-Zn coordination polymers, [{Ru II (bpy) 2 (L2)M II } n ] 4n+ (M ¼ Fe 2+ , Zn 2+ ), were synthesized using the [Ru(bpy) 2 (L2)] 2+ (bpy ¼ 2,2 0 bipyridine) complex as a building block, in which L2 is a bipyridine ligand substituted by two terpyridine sites. The [Ru(bpy) 3 ] 2+ like-subunits provide the assemblies with photoredox properties whereas the second metal allows the build-up of the polymer structure by coordination of the free terpyridine units, associated with additional redox activities. Thin robust films of these metallo supramolecular structures can be easily obtained as a coating on electrode surfaces (C, Pt, and ITO) by a simple electrochemical procedure based on an electroreductive precipitation adsorption process. The morphology of the films has been characterized by AFM. Electrochemical and photophysical properties of these coordination polymers were investigated in CH 3 CN solution as well as thin films deposited on an electrode. The Ru(II)-Zn(II) film, deposited on a transparent ITO electrode, displays luminescence properties. On the other hand, the Ru(II)-Fe(II) film exhibits electrochromic properties under continuous cycling over the Fe II /Fe III and Ru II /Ru III waves, shifting from reddish dark at the Fe(II)-Ru(II) reduced state to orange-yellow at the Fe(III)-Ru(II) state and to pale green at the more oxidized state Fe(III)-Ru(III). These oxidation processes can be also driven by visible light. Indeed, upon continuous irradiation of an CH 3 CN solution of the Ru-Fe polymer in the presence of a diazonium salt as a sacrificial electron acceptor, the fast quantitative one-electron oxidation of the Fe(II) centers followed by that of the Ru(II) ones occurs, despite the strong quenching of the luminescence of the Ru(II) moieties by the Fe(II) center. The photoinduced oxidation of the Fe(II) center is still efficient when the Ru(II)-Fe(II) polymer is electrodeposited as a thin film on ITO leading to the storage of an oxidative equivalent on an electrode. † Electronic supplementary information (ESI) available: Electrochemical behaviour of [Ru(bpy) 2 (L2)] 2+ , [{Ru II -Fe II } n ] 4n+ and [{Ru II -Zn II } n ] 4n+ ; absorption and emission of [{Ru II -Zn II } n ] 4n+ on ITO. See Scheme 1 Chemical structure of the heteroditopic ligands bearing [Ru(bpy) 3 ] 2+ like moieties we have previously developed. 26 9826 | J. Mater. Chem. C, 2014, 2, 9824-9835 This journal is Scheme 2 Chemical formation of [{Ru(bpy) 2 (L2)M} n ] 4n+ (M ¼ Fe, Zn). This journal is

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Section: Introductionmentioning

confidence: 99%

“…The decay is fitted by a biexponential function according to eqn(7). The decay is fitted by a biexponential function according to eqn(7).…”

mentioning

confidence: 99%

Alternated bimetallic [Ru–M] (M = Fe²⁺, Zn²⁺) coordination polymers based on [Ru(bpy)₃]²⁺ units connected to bis-terpyridine ligands: synthesis, electrochemistry and photophysics in solution or in thin film on electrodes

et al. 2014

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“…The characteristic band was observed at 530 nm. This is attributed to the metal-to-ligand chargetransfer band of the 1:2 complex, [Fe(terpy) 2 ] 2 þ (refs 28,29). Interestingly, this meant that the complex [Fe(terpy) 2 ] 2 þ did not form on tp 2 tmp1 but exclusively formed on tp 2 tmp2.…”

mentioning

confidence: 90%

“…Terpy units can be incorporated into any positions in the DNA backbone with these amidite reagents using automated DNA synthesis. Terpy forms a stable complex with Fe 2 þ and some other divalent transition metal ions 28,29 . We expected that the stiffness and conformation of the DNA backbone could be controlled through complexation with certain metal ions.…”

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confidence: 99%

Metal ion-directed dynamic splicing of DNA through global conformational change by intramolecular complexation

et al. 2015

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Chemically engineered DNAs-in which global conformation can be modulated in response to specific stimuli-could be allosteric functional DNAs themselves or work as a modulator of the functional nucleic acids such as DNAzymes and aptamers. Here, we show that two terpyridines built in the DNA backbone form a stable intramolecular 1:2 complex, [M(terpy) 2 ] 2 þ , with divalent transition metal ions. Upon complexation, the DNA conjugates adopt a O-shape structure, in which two distal sequences located outside the terpyridines connect with each other to form a continuous segment with a specific structure or sequence. Such a DNA structure is globally controlled by local metal complexation events that can be rationally designed based on general coordination chemistry. This method is regarded as metal ion-directed dynamic sequence edition or DNA splicing. DNAzymes with peroxidaselike activity can thus be regulated by several transition metal ions through sequence edition techniques based on the O-motif.

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“…Among these, electric and magnetic stimuli-responsive systems have attracted considerable attention because of their easy controllability and industrial needs. Suspensions containing electro-responsive and magneto-responsive particles are often referred to as electrorheological (ER) or magnetorheological (MR) fluids [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25], respectively, in which the ER fluid generally consists OPEN ACCESS of dielectric polarizable particles dispersed in an insulating medium, whereas its magnetic analogue, the MR fluid, is typically based on magnetizable particles dispersed in a carrier medium. When exposed to an electric field, the suspended ER particles become electrically polarized, resulting in the formation of a fibrous structure of originally uniformly distributed particles.…”

Section: Introductionmentioning

confidence: 99%

Stimuli-Responsive Polymers and Colloids under Electric and Magnetic Fields

Zhang¹,

Choi

2014

Polymers

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Electrorheological (ER) and magnetorheological (MR) suspensions undergo a reverse phase transition from a liquid-like to solid-like state in response to an external electric or magnetic field, respectively. This paper briefly reviews various types of electro-or magneto-responsive materials from either polymeric or inorganic and hybrid composite materials. The fabrication strategies for ER/MR candidates and their ER/MR characteristics (particularly for ER fluids) are also included.

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From terpyridine-based assemblies to metallo-supramolecular polyelectrolytes (MEPEs)

Cited by 36 publications

References 122 publications

Alternated bimetallic [Ru–M] (M = Fe²⁺, Zn²⁺) coordination polymers based on [Ru(bpy)₃]²⁺ units connected to bis-terpyridine ligands: synthesis, electrochemistry and photophysics in solution or in thin film on electrodes

Alternated bimetallic [Ru–M] (M = Fe²⁺, Zn²⁺) coordination polymers based on [Ru(bpy)₃]²⁺ units connected to bis-terpyridine ligands: synthesis, electrochemistry and photophysics in solution or in thin film on electrodes

Metal ion-directed dynamic splicing of DNA through global conformational change by intramolecular complexation

Stimuli-Responsive Polymers and Colloids under Electric and Magnetic Fields

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From terpyridine-based assemblies to metallo-supramolecular polyelectrolytes (MEPEs)

Cited by 36 publications

References 122 publications

Alternated bimetallic [Ru–M] (M = Fe2+, Zn2+) coordination polymers based on [Ru(bpy)3]2+ units connected to bis-terpyridine ligands: synthesis, electrochemistry and photophysics in solution or in thin film on electrodes

Alternated bimetallic [Ru–M] (M = Fe2+, Zn2+) coordination polymers based on [Ru(bpy)3]2+ units connected to bis-terpyridine ligands: synthesis, electrochemistry and photophysics in solution or in thin film on electrodes

Metal ion-directed dynamic splicing of DNA through global conformational change by intramolecular complexation

Stimuli-Responsive Polymers and Colloids under Electric and Magnetic Fields

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Product

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Alternated bimetallic [Ru–M] (M = Fe²⁺, Zn²⁺) coordination polymers based on [Ru(bpy)₃]²⁺ units connected to bis-terpyridine ligands: synthesis, electrochemistry and photophysics in solution or in thin film on electrodes

Alternated bimetallic [Ru–M] (M = Fe²⁺, Zn²⁺) coordination polymers based on [Ru(bpy)₃]²⁺ units connected to bis-terpyridine ligands: synthesis, electrochemistry and photophysics in solution or in thin film on electrodes