Multinuclear Magnetic Resonance and DFT Studies of the Poly(chlorotrifluoroethylene-alt-ethyl vinyl ether) Copolymers

Diego Carnevale; Philip Wormald; Bruno Ameduri; Russell Tayouo; Sharon. E. Ashbrook

doi:10.1021/ma900789t

Multinuclear Magnetic Resonance and DFT Studies of the Poly(chlorotrifluoroethylene-alt-ethyl vinyl ether) Copolymers

Diego Carnevale, Philip Wormald, Bruno Ameduri, Russell Tayouo, Sharon. E. Ashbrook

Research output: Contribution to journal › Article › peer-review

Abstract

Chlorotrifluoroethylene (CTFE) and ethyl vinyl ether (EVE) were reacted under radical conditions to produce the poly(CTFE-co-EVE) alternating copolymer, and a full C-13, H-1, and F-19 NMR structural interpretation is offered. All spectra were characterized by broad signals resulting from the overlapping of different chemical shifts. This observation was rationalized by considering a complex mixture of diastereomerically related Compounds, hence allowing an average assignment to be determined. A density functional theory (DFT) Computational study of the isotropic magnetic shieldings with the GIAO and CSGT methods was performed to explore the diasteriomeric relationships between the single building blocks and their mutual influences along the polymer chain. The calculated results totally support the assignment of the experimental chemical shifts of two diasteriomeric sets of resonances indicating chiral center inversion, and not spin-spin J coupling interactions, as the main cause of spectral complexity.

Original language	English
Pages (from-to)	5652-5659
Number of pages	8
Journal	Macromolecules
Volume	42
Issue number	15
DOIs	https://doi.org/10.1021/ma900789t
Publication status	Published - 11 Aug 2009

Keywords

ALTERNATING COPOLYMERIZATION
POLY(VINYLIDENE FLUORIDE)
NMR
F-19
CHLOROTRIFLUOROETHYLENE
GRADIENTS
TELOMERS
H-1-NMR

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@article{8a700b67ba5c43a9be6c4ac655a64ae3,

title = "Multinuclear Magnetic Resonance and DFT Studies of the Poly(chlorotrifluoroethylene-alt-ethyl vinyl ether) Copolymers",

abstract = "Chlorotrifluoroethylene (CTFE) and ethyl vinyl ether (EVE) were reacted under radical conditions to produce the poly(CTFE-co-EVE) alternating copolymer, and a full C-13, H-1, and F-19 NMR structural interpretation is offered. All spectra were characterized by broad signals resulting from the overlapping of different chemical shifts. This observation was rationalized by considering a complex mixture of diastereomerically related Compounds, hence allowing an average assignment to be determined. A density functional theory (DFT) Computational study of the isotropic magnetic shieldings with the GIAO and CSGT methods was performed to explore the diasteriomeric relationships between the single building blocks and their mutual influences along the polymer chain. The calculated results totally support the assignment of the experimental chemical shifts of two diasteriomeric sets of resonances indicating chiral center inversion, and not spin-spin J coupling interactions, as the main cause of spectral complexity.",

keywords = "ALTERNATING COPOLYMERIZATION, POLY(VINYLIDENE FLUORIDE), NMR, F-19, CHLOROTRIFLUOROETHYLENE, GRADIENTS, TELOMERS, H-1-NMR",

author = "Diego Carnevale and Philip Wormald and Bruno Ameduri and Russell Tayouo and Ashbrook, {Sharon. E.}",

year = "2009",

month = aug,

day = "11",

doi = "10.1021/ma900789t",

language = "English",

volume = "42",

pages = "5652--5659",

journal = "Macromolecules",

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TY - JOUR

T1 - Multinuclear Magnetic Resonance and DFT Studies of the Poly(chlorotrifluoroethylene-alt-ethyl vinyl ether) Copolymers

AU - Carnevale, Diego

AU - Wormald, Philip

AU - Ameduri, Bruno

AU - Tayouo, Russell

AU - Ashbrook, Sharon. E.

PY - 2009/8/11

Y1 - 2009/8/11

N2 - Chlorotrifluoroethylene (CTFE) and ethyl vinyl ether (EVE) were reacted under radical conditions to produce the poly(CTFE-co-EVE) alternating copolymer, and a full C-13, H-1, and F-19 NMR structural interpretation is offered. All spectra were characterized by broad signals resulting from the overlapping of different chemical shifts. This observation was rationalized by considering a complex mixture of diastereomerically related Compounds, hence allowing an average assignment to be determined. A density functional theory (DFT) Computational study of the isotropic magnetic shieldings with the GIAO and CSGT methods was performed to explore the diasteriomeric relationships between the single building blocks and their mutual influences along the polymer chain. The calculated results totally support the assignment of the experimental chemical shifts of two diasteriomeric sets of resonances indicating chiral center inversion, and not spin-spin J coupling interactions, as the main cause of spectral complexity.

AB - Chlorotrifluoroethylene (CTFE) and ethyl vinyl ether (EVE) were reacted under radical conditions to produce the poly(CTFE-co-EVE) alternating copolymer, and a full C-13, H-1, and F-19 NMR structural interpretation is offered. All spectra were characterized by broad signals resulting from the overlapping of different chemical shifts. This observation was rationalized by considering a complex mixture of diastereomerically related Compounds, hence allowing an average assignment to be determined. A density functional theory (DFT) Computational study of the isotropic magnetic shieldings with the GIAO and CSGT methods was performed to explore the diasteriomeric relationships between the single building blocks and their mutual influences along the polymer chain. The calculated results totally support the assignment of the experimental chemical shifts of two diasteriomeric sets of resonances indicating chiral center inversion, and not spin-spin J coupling interactions, as the main cause of spectral complexity.

KW - ALTERNATING COPOLYMERIZATION

KW - POLY(VINYLIDENE FLUORIDE)

KW - NMR

KW - F-19

KW - CHLOROTRIFLUOROETHYLENE

KW - GRADIENTS

KW - TELOMERS

KW - H-1-NMR

U2 - 10.1021/ma900789t

DO - 10.1021/ma900789t

M3 - Article

SN - 0024-9297

VL - 42

SP - 5652

EP - 5659

JO - Macromolecules

JF - Macromolecules

IS - 15

ER -

Multinuclear Magnetic Resonance and DFT Studies of the Poly(chlorotrifluoroethylene-alt-ethyl vinyl ether) Copolymers

Abstract

Keywords

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