Synthesis and characterization of soluble polymers containing electron- and energy-transfer reagents

Younathan, Janet N.; McClanahan, Stephen F.; Meyer, Thomas J.

doi:10.1021/ma00193a009

Cited by 48 publications

(17 citation statements)

References 6 publications

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“…[55] They used the nucleophilic displacement of chloro substituents from poly(m(p)-(chloromethyl)styrenestat-styrene) with alkoxide or carboxylate nucleophiles, under concomitant formation of amide and ether linkages (Figure 11). In the case of pendant bipyridine complexes, the corresponding unsymmetrically functionalized tris(bipyridine)ruthenium(ii) complex was used as a nucleophile.…”

Section: Polymers With Bipyridine Units In the Side Chainmentioning

confidence: 99%

Macromolecules Containing Bipyridine and Terpyridine Metal Complexes: Towards Metallosupramolecular Polymers

Schubert

Eschbaumer

2002

Angew. Chem. Int. Ed.

691

333

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The ability of a broad range of N-heterocycles to act as very effective and stable complexation agents for several transition metal ions, such as cobalt(II), copper(II), nickel(II), and ruthenium(II), has long been known in analytical chemistry. This behavior was later utilized in supramolecular chemistry for the construction of highly sophisticated architectures, such as helicates, racks, and grids. The discovery of macromolecules by Staudinger in 1922 opened up avenues towards sophisticated materials with properties hitherto completely unknown. In the last few decades, the combination of macromolecular and supramolecular chemistry has been attempted by developing metal-complexing and metal-containing polymers for a wide variety of applications that range from filtration to catalysis. The stability of the polymer-metal complex is a fundamental requirement for such applications. In this respect, the use of bi- and terpyridines as chelating ligands is highly promising, since these molecules are known to form highly stable complexes with interesting physical properties with transition-metal ions. A large number of different structures have been designed for many different applications, but polymers based on the application of coordinative forces have been prepared in a few cases only. Furthermore, the synthetic procedures applied frequently resulted in low yields. During the last few years, strong efforts have been made in the direction of self-assembling and supramolecular polymers as novel materials with "intelligent" and tunable properties. In this review, an overview of this active area at the interface of supramolecular and macromolecular chemistry is given.

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Section: Polymers With Bipyridine Units In the Side Chainmentioning

confidence: 99%

Macromolecules Containing Bipyridine and Terpyridine Metal Complexes: Towards Metallosupramolecular Polymers

Schubert

Eschbaumer

2002

Angew. Chem. Int. Ed.

691

333

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“…Our research group has been interested in developing polymerization strategies to prepare functionalized polystyrenes that feature pendant metal–organic chromophores and to investigate the photophysical and electrochemical properties of the chromophoric sites preserved in the polymer. As an early synthetic strategy, polymer assemblies containing a [tris(bipyridyl)ruthenium(II) derivatives] were considered for creating polymer assemblies that could be modified by introducing polypyridyl Ru complexes [ 24 , 25 , 34 ].…”

Section: Polymer-based Metal Complex Assembliesmentioning

confidence: 99%

“…Polypyridyl complexes of ruthenium were attached to styrene- p -(chloromethyl) styrene copolymers derivatized via nucleophilic displacement of chloride followed by the formation of an ether ( 1 ) or ester linkage ( 2 ) in Table 1 [ 24 ]. Based on electronic absorption spectral data of ether and amide-linked polymers, the photophysical properties of the metal to ligand charge-transfer transitions of ruthenium(II) complexes on the polymeric chain are unchanged upon binding to the polymers.…”

Section: Polymer-based Metal Complex Assembliesmentioning

confidence: 99%

Polymer-based chromophore–catalyst assemblies for solar energy conversion

2017

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The synthesis of polymer-based assemblies for light harvesting has been motivated by the multi-chromophore antennas that play a role in natural photosynthesis for the potential use in solar conversion technologies. This review describes a general strategy for using polymer-based chromophore–catalyst assemblies for solar-driven water oxidation at a photoanode in a dye-sensitized photoelectrochemical cell (DSPEC). This report begins with a summary of the synthetic methods and fundamental photophysical studies of light harvesting polychormophores in solution which show these materials can transport excited state energy to an acceptor where charge-separation can occur. In addition, studies describing light harvesting polychromophores containing an anchoring moiety (ionic carboxylate) for covalent bounding to wide band gap mesoporous semiconductor surfaces are summarized to understand the photophysical mechanisms of directional energy flow at the interface. Finally, the performance of polychromophore/catalyst assembly-based photoanodes capable of light-driven water splitting to oxygen and hydrogen in a DSPEC are summarized.

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“…Meyer et al stellten redoxaktive Polymere vor, die [Ru(bpy) 3 ]‐Komplexe als Chromophore enthielten und sichtbares Licht absorbierten 55. Nach nucleophiler Substitution der Chlorsubstituenten in Poly( m ( p )‐(chlormethyl)styrol‐ stat ‐styrol) durch Alkoxide oder Amine wurden die Chromophore unter Bildung von Ether oder Amidgruppen an das Polymer gebunden (Abbildung 11).…”

Section: Makromoleküle Mit Bipyridinligandenunclassified

“… Polystyrole mit Bipyridin‐Ruthenium‐ und Bipyridin‐Osmiumkomplexen in der Seitenkette als Energietransferreagentien 55–61…”

Section: Makromoleküle Mit Bipyridinligandenunclassified

MakromolekÃ¼le mit Bipyridin- und Terpyridinkomplexen als VerknÃ¼pfungsstellen: erste Schritte auf dem Weg zu metallo-supramolekularen Polymeren

2002

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Die Fähigkeit von Stickstoffheterocyclen, Übergangsmetallionen wie Cobalt(II), Kupfer(II), Nickel(II) und Ruthenium(ii) außerordentlich effektiv und stabil zu komplexieren, wird schon seit langem in der Analytischen Chemie angewendet. In der Supramolekularen Chemie nutzte man später diese Eigenschaft zum Aufbau anspruchsvoller Strukturen wie Helicate, Leitern oder Gitter. Die Entdeckung der Makromoleküle durch Staudinger eröffnete bereits 1922 den Zugang zu einer Materialklasse mit bis dahin völlig unbekannten Eigenschaften. Erst in den letzten Jahrzehnten jedoch wurde versucht, die Makromolekulare und Supramolekulare Chemie durch die Entwicklung von metallkomplexierenden und metallhaltigen Polymeren mit Anwendungen von der Filtration bis zur Katalyse zu vereinen. Die entscheidende Anforderung an Materialien für solche Anwendungen ist die Stabilität der Polymer‐Metallkomplexe. Besonders vielversprechend ist die Verwendung der mehrzähnigen Bipyridin‐ und Terpyridin‐Chelatliganden, die sehr stabile Übergangsmetallkomplexe mit beeindruckenden physikalischen Eigenschaften bilden. Ein breites Spektrum an Strukturen ist für eine ebenso umfangreiche Zahl von Anwendungen entwickelt worden. Die Synthese von Polymeren auf Basis koordinativer Wechselwirkungen wurde dagegen bis vor wenigen Jahren nur in sehr wenigen Fällen realisiert und führte darüber hinaus häufig zu geringen Ausbeuten. In den vergangenen Jahren jedoch erlebte die Forschung zu selbstorganisierten und supramolekularen Polymeren als neue, „intelligente“ Materialien mit einstellbaren Eigenschaften einen Höhenflug. In diesem Aufsatz geben wir einen Überblick über dieses Gebiet an der Schnittstelle von Supramolekularer und Makromolekularer Chemie.

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Synthesis and characterization of soluble polymers containing electron- and energy-transfer reagents

Cited by 48 publications

References 6 publications

Macromolecules Containing Bipyridine and Terpyridine Metal Complexes: Towards Metallosupramolecular Polymers

Macromolecules Containing Bipyridine and Terpyridine Metal Complexes: Towards Metallosupramolecular Polymers

Polymer-based chromophore–catalyst assemblies for solar energy conversion

MakromolekÃ¼le mit Bipyridin- und Terpyridinkomplexen als VerknÃ¼pfungsstellen: erste Schritte auf dem Weg zu metallo-supramolekularen Polymeren

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