Poly(bisnorbornanediol)

Lin, Neng-Yu; Lee, Sherng-Long; Yu, Jianyuan; Chen, Chun‐hsien; Huang, Shou‐Ling; Luh, Tien‐Yau

doi:10.1021/ma901302e

Cited by 13 publications

(7 citation statements)

References 34 publications

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“…Luh et al reported a series of interesting structural analogues of DNA derived from a fully artificial framework. , Ring-opening metathesis polymerizations of bisnorbornene derivatives bearing a ferrocene spacer produced double-stranded ladder polymers ( 531a and 532 – 534 in Chart ). − Scanning tunneling microscopy (STM) investigations revealed a double-helical structure of 531a , whose geometric parameters, such as helical pitch, are very similar to those of the natural DNA . An excess one-handed double-helical ladder polymer ( 529a and 530a ) has also been synthesized by incorporating stereogenic centers in the ferrocene spacer .…”

Section: Helical Polymers and Their Assembliesmentioning

confidence: 99%

Supramolecular Helical Systems: Helical Assemblies of Small Molecules, Foldamers, and Polymers with Chiral Amplification and Their Functions

et al. 2016

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In this review, we describe the recent advances in supramolecular helical assemblies formed from chiral and achiral small molecules, oligomers (foldamers), and helical and nonhelical polymers from the viewpoints of their formations with unique chiral phenomena, such as amplification of chirality during the dynamic helically assembled processes, properties, and specific functionalities, some of which have not been observed in or achieved by biological systems. In addition, a brief historical overview of the helical assemblies of small molecules and remarkable progress in the synthesis of single-stranded and multistranded helical foldamers and polymers, their properties, structures, and functions, mainly since 2009, will also be described.

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Section: Helical Polymers and Their Assembliesmentioning

confidence: 99%

Supramolecular Helical Systems: Helical Assemblies of Small Molecules, Foldamers, and Polymers with Chiral Amplification and Their Functions

et al. 2016

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“…The double bonds in 48 undergo dihydroxylation with OsO 4 under Narasaka conditions giving the corresponding polyboronate 49, which is transesterified into 50 (Scheme 4). 71 The STM image of 50 on HOPG (Figure 8a) shows that polymers with equal lengths tend to align together, presumably due to full usage of all available hydroxyl groups on the polymeric backbones for hydrogen bonding. Unlike ladderphanes with vinyl and styrene end groups, adjacent molecules of 50 are assembled in staggered form along the longitudinal direction.…”

Section: With Alicyclicmentioning

confidence: 99%

Ladderphanes: A New Type of Duplex Polymers

Luh

2012

Acc. Chem. Res.

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A polymeric ladderphane is a step-like structure comprising multiple layers of linkers covalently connected to two or more polymeric backbones. The linkers can be planar aromatic, macrocyclic metal complexes, or three-dimensional organic or organometallic moieties. Structurally, a DNA molecule is a special kind of ladderphane, where the cofacially aligned base-pair pendants are linked through hydrogen bonding. A greater understanding of this class of molecules could help researchers develop new synthetic molecules capable of a similar transfer of chemical information. In this Account, we summarize our studies of the strategy, design, synthesis, characterization, replications, chemical and photophysical properties, and assembly of a range of double-stranded ladderphanes with many fascinating structures. We employed two norbornene moieties fused with N-arylpyrrolidine to connect covalently with a range of relatively rigid linkers. Ring opening metathesis polymerizations (ROMP) of these bis-norbornenes using the first-generation Grubbs ruthenium-benzylidene catalyst produced the corresponding symmetrical double-stranded ladderphanes. The N-arylpyrrolidene moiety in the linker controls the isotactic selectivity and the trans configuration for all double bonds in both single- and double-stranded polynorbornenes. The π-π interactions between these aryl pendants may contribute to the high stereoselectivity in the ROMP of these substrates. We synthesized chiral helical ladderphanes by incorporating asymmetric center(s) in the linkers. Replication protocols and sequential polymerization of a monomer that includes two different polymerizable groups offer methods for producing unsymmetical ladderphanes. These routes furnish template synthesis of daughter polymers with well-controlled chain lengths and polydispersities. The linkers in these ladderphanes are well aligned in the center along the longitudinal axis of the polymer. Fluorescence quenching, excimer formation, or Soret band splitting experiments suggest that strong interactions take place between the linkers. The antiferromagnetism of the oxidized ferrocene-based ladderphanes further indicates strong coupling between linkers in these ladderphanes. These polynorbornene-based ladderphanes can easily aggregate to form a two-dimensional, highly ordered array on the graphite surface with areas that can reach the submicrometer range. These morphological patterns result from interactions between vinyl and styryl end groups via π-π stacking along the longitudinal axis of the polymer and van der Waals interaction between backbones of polymers. Such assembly orients planar arene moieties cofacially, and polynorbornene backbones insulate each linear array of arenes from the adjacent arrays. Dihydroxylation converts the double bonds in polynorbornene backbones of ladderphanes into more hydrophilic polyols. Hydrogen bonding between these polyol molecules leads to self-assembly and produces structures with longitudinally staggered morphologies on the graphite surface.

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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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Poly(bisnorbornanediol)

Cited by 13 publications

References 34 publications

Supramolecular Helical Systems: Helical Assemblies of Small Molecules, Foldamers, and Polymers with Chiral Amplification and Their Functions

Supramolecular Helical Systems: Helical Assemblies of Small Molecules, Foldamers, and Polymers with Chiral Amplification and Their Functions

Ladderphanes: A New Type of Duplex Polymers

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

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