Macromolecules Containing Redox-Active Neutral and Cationic Iron Complexes

Agatemor

Etkin

et al. 2016

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Photoactive materials are actively researched, piloting breakthroughs that have enriched fundamental understanding of science, and have led to real applications. Tetraphenylethene, a photoactive molecule that is of interest from fundamental and applied perspectives, features photochemical properties that are not exploited in the design of photoactive, dual-emissive materials. Here, tetraphenylethene-based, dual-emissive dendrimers are constructed via a synthetic approach that involves a photochemical reaction that exploits the photochemistry of tetraphenylethene. These dendrimers are emissive in solution and in the aggregate state with tunable dual emissions at 368 and 469 nm. The photochemical reaction also tunes the size of the aggregates, increasing the size after UV irradiation. The reported synthetic strategy is a direct and facile approach to accessing dual-emissive macromolecules, especially tetraphenylethene-based systems for real applications.

Section: Resultsmentioning

confidence: 99%

Photoinduced Synthesis of Dual‐Emissive Tetraphenylethene‐Based Dendrimers with Tunable Aggregates and Solution States Emissions

Agatemor

Etkin

et al. 2016

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“…Like other macromolecules, sandwich complex‐containing macromolecules can be obtained through step polymerization mechanisms, which include esterification, hydrosilylation, amidation, and aromatic substitution, as well as other substitution reactions. These step polymerization reactions offer the opportunity to tune the properties of the sandwich complex‐containing macromolecule through the incorporation of various spacers . Electronics as well as the structure of the spacers tunes electronic interaction between the metal centers, solubility, and thermal properties of the resulting polymer.…”

Section: Macromolecules Bearing Sandwich Complexes In the Main Chainmentioning

confidence: 99%

“…In the cationic η 6 ‐aryl‐ η 5 ‐cyclopentadienyliron(II) sandwich complex, the electron‐withdrawing effect of the CpFe + moiety on the arene ring renders the latter susceptible to nucleophilic addition and substitution reactions. These reactions allow access to η 6 ‐aryl‐ η 5 ‐cyclopentadienyliron(II)‐containing polyethers, polythioethers, and polyamines under mild reaction conditions . Recently, Abd‐El‐Aziz and co‐workers reported a polyether that featured two cationic η 6 ‐aryl‐ η 5 ‐cyclopentadienyliron(II) moieties and a pendant 2‐(3‐thienyl)ethylpropanoate or 2,3‐dihydrothieno[3,4‐b][1,4]dioxin‐2‐ylmethyl‐propanoate per monomer unit .…”

Section: Macromolecules Bearing Sandwich Complexes In the Main Chainmentioning

confidence: 99%

“…Previously, the Abd‐El‐Aziz group employed a nucleophilic aromatic substitution reaction to synthesize a series of macromolecules. These macromolecules had two cationic η 6 ‐aryl‐ η 5 ‐cyclopentadienyliron moieties with or without a neutral ferrocene moiety within a monomer unit in the main chain . The monomers were linked via a 4,4′‐thiobisbenzene, 1,8‐octanedithiol, or hydroquinone spacer.…”

Section: Macromolecules Bearing Sandwich Complexes In the Main Chainmentioning

confidence: 99%

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Sandwich Complex‐Containing Macromolecules: Property Tunability Through Versatile Synthesis

Agatemor

Etkin

2014

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Sandwich complexes feature unique properties as the physical and electronic properties of a hydrocarbon ligand or its derivative are integrated into the physical, electronic, magnetic, and optical properties of a metal. Incorporation of these complexes into macromolecules results in intriguing physical, electrical, and optical properties that were hitherto unknown in organic-based macromolecules. These properties are tunable through well-designed synthetic strategies. This review surveys many of the synthetic approaches that have resulted in tuning the properties of sandwich complex-containing macromolecules. While the past two decades have seen an ever-growing number of research publications in this field, gaps remain to be filled. Thus, we expect this review to stimulate research interest towards bridging these gaps, which include the insolubility of some of these macromolecules as well as expanding the scope of the sandwich complexes.

“…[23][24][25] Incorporation of cationic cyclopentadienyliron moieties into macromolecules can increase the solubility of the materials compared to their organic analogues and can give electrocatalytic properties. [26] The incorporation of cationic arenecoordinated cyclopentadienyliron complexes onto the upper rim of calix [4]arenes should give materials that combine the guest-host chemistry and ion trapping of calix [4]arenes, with the electrochemical properties of cationic cyclopentadienyliron. Controlled design of the organoiron complex allows for organoiron mediated synthesis of larger molecules.…”

Section: Introductionmentioning

confidence: 99%

Design of Organoiron Macromolecules Based on Upper Rim Functionalized Calix[4]arenes

Shipman

Shipley

2010

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The versatility of cationic cyclopentadienyliron complexes is demonstrated for the generation of calix[4]arene-based dendrimers and polymers. Dendrimers were prepared from a branched organoiron calix[4]arene through subsequent reactions of azo dyes and organoiron complexes. The resulting azo dye-containing metallocalix[4]arenes were soluble in polar organic solvents and displayed λ(max) ranging between 430 and 456 nm. Upon addition of various acids, the λ(max) shifted to higher wavelengths (513-535 nm). In the solid state and in solution, the azo dye-containing metallocalix[4]arenes reversibly changed colour in the presence of acid and base, indicating their potential use as acid sensors. Cyclic voltammetric studies showed that the iron centres of the metallocalix[4]arenes were reversibly reduced at E(1/2) = -1.49 V. When non-branching organoiron-based calix[4]arene were reacted with dithiols, polymers containing calix[4]arenes either in their side chains or main chains were obtained. The polymers possessed weight average molecular weights between 35 000 and 53 000. The polymers were determined to be thermally stable with backbone decomposition occurring above 500 °C.