Ring opening metathesis polymerization of bisnorbornene derivatives linked by Cp2Ni2(μ-S)2 bridge

Yang, Hui‐Chun; Lin, Shiu-Mei; Liu, Yi-Hung; Wang, Yu; Chen, Mei-Man; Sheu, Hwo‐Shuenn; Tsou, D.T.; Lin, Chih‐Hsiu; Luh, Tien‐Yau

doi:10.1016/j.jorganchem.2006.03.041

Cited by 20 publications

(16 citation statements)

References 18 publications

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“…It has found a tremendous utility for the synthesis of materials having specific biological, electronic, and mechanical properties. In 1992, the living ROMP was first applied to prepare well-defined side chain ferrocene containing polymers and block copolymers by Schrock and co-workers, who used the molybdenum-based metathesis catalyst [Mo(CH- t -Bu)(NAr)(O- t -Bu) 2 ] (Figure ). − Since then, the groups of Mirkin, − Abd-El-Aziz, − and Luh − prepared a series of side chain ferrocene containing polynorbornene homopolymers and block copolymers by ROMP. The most frequently used catalysts were ruthenium-based Grubbs first- and second-generation catalysts (Figure ) .…”

Section: Introductionmentioning

confidence: 99%

Living Ring-Opening Metathesis–Polymerization Synthesis and Redox-Sensing Properties of Norbornene Polymers and Copolymers Containing Ferrocenyl and Tetraethylene Glycol Groups

Rapakousiou

Castel

et al. 2014

Organometallics

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The controlled synthesis of monodisperse, redox-active metallopolymers and their redox properties and functions, including robust electrode derivatization and sensing, remains a challenge. Here a series of polynorbornene homopolymers and block copolymers containing side-chain amidoferrocenyl groups and tetraethylene glycol linkers were prepared via living ring-opening metathesis polymerization initiated by Grubbs’ third-generation catalyst (1). Their molecular weights were determined using MALDI-TOF mass spectra, size exclusion chromatography (SEC), end-group analysis, and the empirical Bard–Anson electrochemical equation. All polymerizations followed a living and controlled manner, and the number of amidoferrocenyl units varied from 5 to 332. These homopolymers and block copolymers were successfully used to prepare modified Pt electrodes that showed excellent stability. The modified Pt electrodes show excellent qualitative sensing of ATP2– anions, in particular those prepared with the block copolymers. The quantitative recognition and titration of [n-Bu4N]2[ATP] was carried out using the CH2Cl2 solution of the homopolymers, showing that two amidoferrocenyl groups of the homopolymers interacted with each ATP2– molecule. This stoichiometry led us to propose the H-bonding modes in the supramolecular polymeric network.

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Section: Introductionmentioning

confidence: 99%

Living Ring-Opening Metathesis–Polymerization Synthesis and Redox-Sensing Properties of Norbornene Polymers and Copolymers Containing Ferrocenyl and Tetraethylene Glycol Groups

Rapakousiou

Castel

et al. 2014

Organometallics

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“…Conformational disorder arising from rotatory single bonds may lead to irregular microstructures on the backbone. The control over the position of pendants in two-dimensions relies on the use of a more rigid scaffolds including oligoproline, nucleic acid, polyisocyanides and polynorbornenes. ,− Accordingly, interactions between pendant chromophores would be more efficient if they could be better aligned along polymeric backbone.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, polynorbornenes 1 obtained from ring-opening metathesis polymerization (ROMP) of norbornenes fused with endo-N-arylpyrrolidine moiety 2 have been shown to have isotactic stereochemistry with all pendants aligned toward a similar direction like a Chinese folded fan (eq 1). These unique topological features have facilitated the successful synthesis of polynorbornene-based ladderphanes − and replication of single stranded polynorbornenes into corresponding daughter polymers . The spacing separating adjacent monomeric units for these polynorbornenes is about 5.5 Å .…”

Section: Introductionmentioning

confidence: 99%

“…The spacing separating adjacent monomeric units for these polynorbornenes is about 5.5 Å . Interactions between neighboring pendants or linkers can be discerned by various spectroscopic means. − Fluorescence quenching, ,, excimer formation, Soret band splitting, ,, and enhancement of chiroptical properties ,, and second order optical nonlinearity are frequently observed in these polynorbornene-based polymers.…”

Section: Introductionmentioning

confidence: 99%

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Controlling the Orientation of Pendants in Two-Dimensional Comb-Like Polymers by Varying Stiffness of Polymeric Backbones

et al. 2014

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The electronic communications between chromophores are closely related to distances and orientation of these π-conjugated systems. Reported herein is a collection of well-defined two-dimensional comb-like polymers containing porphyrin pendants obtained by ring-opening metathesis polymerizations of norbornene and cyclobutene derivatives using ruthenium or molybdenum catalysts. The spacing separating the adjacent pendants are defined by ring sizes of cycloalkenes and the orientations are determined by the stiffness of the polymeric backbone, which is, in turn, discerned by the percentage of Z-double bonds. Both peak widths of the porphyrin radical cation of the EPR spectra and the absorption profiles in the Soret band region reflect the degree of the spin delocalization and exciton coupling between porphyrin pendants in these polymers and, hence, the stiffness of the polymeric backbone. Our approach offers a useful protocol to align an array of chromophores appended onto a rigid polymeric backbone so that the optoelectronic properties can be tuned.

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“…[4,54,55] However, it is puzzling that submicron-long strings are sometimes observed from dropcast films. [3][4][5]50] Such extraordinary long features were previously ascribed to those significantly deviated from the average molecular weight.…”

Section: Introductionmentioning

confidence: 99%

Oligomeric Tectonics: Supramolecular Assembly of Double‐Stranded Oligobisnorbornene through π–π Stacking

Lee

Lin

Liao

et al. 2009

Chemistry A European J

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Self-assembly at the molecular level in solutions or on a surface is a subject of current interest. Herein we describe the tailoring of oligobisnorbornene 1, which represents an innovative concept of a preorganized building block on the tens of nanometer scale. The rodlike 1 has vinyl and styrenyl end groups. Scanning tunneling microscopy (STM) reveals that the oligomers aggregate anisotropically along the long axis and form a one-dimensional assembly in which, remarkably, no interstitial gap appears between neighboring oligomers. Dynamic light-scattering (DLS) measurements indicate that the assembly develops in solution. With a shear treatment for dropcast films, a unidirectionally ordered domain with a defect density less than 0.5 % can be prepared. Simulation results by molecular dynamics suggest that there may be multiple interactions such as pi-pi stacking and dipolar attractions taking place between the termini of the oligomers. To demonstrate the importance of double bonds in the oligomeric backbones and termini towards the tectonic assembly, a hydrogenated analogue was synthesized; pi-pi interactions are thus less significant and the film morphology is completely different from that of 1. This work extends the concept of molecular tectonics to preorganized oligomers and opens up a new avenue of nanopatterning toward nanodevices.

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Ring opening metathesis polymerization of bisnorbornene derivatives linked by Cp2Ni2(μ-S)2 bridge

Cited by 20 publications

References 18 publications

Living Ring-Opening Metathesis–Polymerization Synthesis and Redox-Sensing Properties of Norbornene Polymers and Copolymers Containing Ferrocenyl and Tetraethylene Glycol Groups

Living Ring-Opening Metathesis–Polymerization Synthesis and Redox-Sensing Properties of Norbornene Polymers and Copolymers Containing Ferrocenyl and Tetraethylene Glycol Groups

Controlling the Orientation of Pendants in Two-Dimensional Comb-Like Polymers by Varying Stiffness of Polymeric Backbones

Oligomeric Tectonics: Supramolecular Assembly of Double‐Stranded Oligobisnorbornene through π–π Stacking

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