Ein optisch aktives Polyamid mit atropisomeren Binaphthyl‐Grundbausteinen

Schulz, Von Rolf C.; Jung, Rudolf H.

doi:10.1002/macp.1968.021160119

Cited by 39 publications

(20 citation statements)

References 6 publications

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“…Several research groups have already proven helical structures for different poly(amide)s from atropisomeric monomers based on CD investigations. [13][14][15] The chiral character of (þ)BINAM-PMDA was proven by CD measurements (Figure 2). The presence of chiral molecules influences the optical rotation of the polymer, as presumably best known from peptide chemistry.…”

Section: General Polymer Characterisation and Structure Analysismentioning

confidence: 99%

Towards Chiral Microporous Soluble Polymers—Binaphthalene‐Based Polyimides

Ritter

Senkovska

Kaskel

et al. 2011

Macromol. Rapid Commun.

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Recently, intrinsically microporous polymers have received increased interest in research. Contrary to currently commercially used microporous materials, e.g., zeolithes or polymer networks, they can be dissolved, processed and further functionalized. Microporous poly(imide)s are especially interesting, as they are chemically and thermally resistant to decomposition up to high temperatures. In this paper, we report for the first time on a chiral poly(imide) which is intrinsically microporous and soluble in common solvents. After analysing the structure of the polymer, its pore system is characterised via its ability to adsorb nitrogen, argon, hydrogen and carbon dioxide. Furthermore, the chiral polymer is compared with its racemic counterpart, illustrating the special role of an organised superstructure.

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Section: General Polymer Characterisation and Structure Analysismentioning

confidence: 99%

Towards Chiral Microporous Soluble Polymers—Binaphthalene‐Based Polyimides

Ritter

Senkovska

Kaskel

et al. 2011

Macromol. Rapid Commun.

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show abstract

“…7 Due to their structural rigidity, simplicity, conjugated -systems, axial chirality, and chiroptical behaviors, many attempts have recently been reported to synthesize optically active polymers from the functionalized 1,1Ј-binaphthyls. A variety of chiral binaphthyl monomers such as 1,1Ј-bi-2-naphthol 8 and thereof derived dibromides, 9 diacetylenes 10 and diethylenes, 11 bis(oxazolines), 12 1,1Ј-binaphthyl-2,2Ј-diamine, 13 and 1,1Ј-binaphthalene-2,2Ј-dicarboxylic acid, 14 etc., have been synthesized. In our previous papers 15 2,2Ј-bis(3,4-dicarboxyphenoxy)-1,1Ј-binaphthyl dianhydride was synthesized, and optically active aromatic poly(ether imide)s were obtained from this dianhydride.…”

Section: Introductionmentioning

confidence: 99%

Optically active poly(amide-imide)s containing axially dissymmetric 1,1?-binaphthyl moieties

Song

Gao

Ding

1999

J. Polym. Sci. A Polym. Chem.

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Novel optically active aromatic poly(amide–imide)s (PAIs) were prepared from newly synthesized 2,2′‐bis(3,4‐dicarboxybenzamido)‐1,1′‐binaphthyl dianhydride ((+)‐, (S)‐, and (R)‐BNDADA). PAIs based on dianhydride monomers with different ee % were investigated with respect to their structures and chiroptical properties. These polymers were highly soluble in polar aprotic solvents such as N,N‐dimethylacetamide, N‐methyl‐2‐pyrrolidone, pyridine, etc., and showed high glass transition temperatures of 287–290°C and 5% weight loss temperatures of 450–465°C in nitrogen. Optically active PAIs exhibited high specific rotations, excellent optical stabilities, and a dependence of optical activities on temperature. Investigations on chiroptical properties indicated that chiral conformation was possessed by optically active PAIs. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3147–3154, 1999

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“…The polycondensation of (R)-(+)-1,1 -binaphthyl-2,2 -diamine with terephthaloyl chloride was first reported by Schulz and Jung over thirty years ago. 1 The resulting polyaramide exhibited significant optical rotatory power that was attributed to the presence of a single helical screw sense along the polymer's conformationally restricted backbone. In the decades that have followed, a variety of other optically active macromolecules have been assembled from atropisomeric, helix-directing monomers using this same generalized approach.…”

mentioning

confidence: 99%

Stimuli-Responsive Polymers VI. Azobenzene Modified Copolyaramides with Chiral Helical Geometries: Influence of Rigid, Helix-Disrupting Segments on Physiochemical and Chiroptical Behavior

Jaycox

2002

Polym J

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ABSTRACT:Polymers comprised of alternating trans-4,4 -azobenzene and helix directing (R)-2,2 -binaphthylene backbone linkages adopt single handed helical conformations in solution that are reversibly distorted by light and heat regulated trans ↔ cis isomerization processes. The replacement of (R)-binaphthylene backbone groups with helixdisrupting 4,4 -diphenylfluorene segments affords permanent changes in some of the properties exhibited by this family of optically active materials. Polymer solubilities in organic solvents like THF and acetone are significantly diminished while thermal stabilities and photophysical behavior remain largely unchanged. Optical rotation magnitudes measured at the sodium D-line drop in a linear manner with the loss of the atropisomeric binaphthylene linkages. However, all of the polymer variants exhibit stimuli-responsive chiroptical behavior when evaluated in DMAC or THF solution environments. Specific rotation magnitudes are reversibly diminished by the near-UV light induced trans → cis isomerization reaction. Optical rotatory power is restored by reverse cis → trans isomerization processes triggered by heat or by visible light illumination. That stimuli-responsive chiroptical properties are exhibited by all polymer variants regardless of their monomer compositions indicates that global helical order along the polymer backbone is not necessarily required for this effect. Rather, isomerization induced perturbations to the local dihedral angles residing in the atropisomeric binaphthylene main chain segments likely serve as the genesis for photo-and thermo-regulated behavior in these materials.KEY WORDS Stimuli-Responsive Chiroptical Behavior / trans-cis Azobenzene Isomerization / Helical Polymers / Circular Dichroism / Optical Rotation / Exciton Coupling / Cardo Polymers / Macromolecules endowed with single-handed helical geometries can be prepared by a variety of synthetic methods. Monomers based on chiral 1,1 -binaphthylenes, 1,1 -biphenylenes and other axially dissymmetric ring systems provide convenient access to condensation polymers with chiral helical motifs. The polycondensation of (R)-(+)-1,1 -binaphthyl-2,2 -diamine with terephthaloyl chloride was first reported by Schulz and Jung over thirty years ago. 1 The resulting polyaramide exhibited significant optical rotatory power that was attributed to the presence of a single helical screw sense along the polymer's conformationally restricted backbone. In the decades that have followed, a variety of other optically active macromolecules have been assembled from atropisomeric, helix-directing monomers using this same generalized approach. 2 Earlier, this laboratory reported the preparation of a number of helical trans-azobenzene modified polyaramides from both (R)-and (S )-1,1 -binaphthyl-2,2 -diamine. 3, 4 Some of these materials were specifically designed to undergo reversible helix order ↔ disorder transitions in response to multiple trans ↔ cis azobenzene isomerization reactions triggered within the polymer's main chain. [5]...

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Ein optisch aktives Polyamid mit atropisomeren Binaphthyl‐Grundbausteinen

Cited by 39 publications

References 6 publications

Towards Chiral Microporous Soluble Polymers—Binaphthalene‐Based Polyimides

Towards Chiral Microporous Soluble Polymers—Binaphthalene‐Based Polyimides

Optically active poly(amide-imide)s containing axially dissymmetric 1,1?-binaphthyl moieties

Stimuli-Responsive Polymers VI. Azobenzene Modified Copolyaramides with Chiral Helical Geometries: Influence of Rigid, Helix-Disrupting Segments on Physiochemical and Chiroptical Behavior

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