Spectroscopic Characterization of Novel Polycyclic Aromatic Polymers

O’Neill, Luke A.J.; Lynch, Patrick; McNamara, Mary; Byrne, Hugh J.

doi:10.1021/jp0662754

Cited by 8 publications

(20 citation statements)

References 22 publications

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“…4. The emission of POPV was recorded at 550 nm, which had been established as the peak emission wavelength [17]. A deconvolution fit gives a lifetime of 1.16 ns for the POPV polymer.…”

Section: Resultsmentioning

confidence: 99%

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Correlation of vibrational intensity with fluorescence lifetimes in π conjugated polymers

O’Neill¹,

Lynch²,

McNamara³

et al. 2008

Polymer

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a b s t r a c tA series of novel pi (p) conjugated polymers, originating from the archetypical Polyphenylene vinylene, in which the phenyl units are successively replaced by the larger naphthyl and anthryl acene units, were previously found to have a well-defined relationship between their relative fluorescence yields and their vibrational characteristics, as determined by Raman spectroscopy. In this study the Strickler-Berg equation is used to probe the influence of continual substitution of higher order acene units into the conjugated backbone in terms of the variation of the radiative and non-radiative rates. The deconvolution of the radiative and non-radiative rates enables the correlation of the reduction of the Raman intensity and concomitant increase in the fluorescence yield with the reduction of the non-radiative rate. This confirms that the reduction of the non-radiative rate is the dominant process introduced by the vibrational confinement originating from systematic substitution of higher order acene units into the polymer backbone.

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“…4. The emission of POPV was recorded at 550 nm, which had been established as the peak emission wavelength [17]. A deconvolution fit gives a lifetime of 1.16 ns for the POPV polymer.…”

Section: Resultsmentioning

confidence: 99%

“…1, it has been demonstrated that both the electronic and vibrational activities of these complex systems can be controlled and optimized by systematic variation of the polymer conjugated backbone [17,18].…”

Section: Introductionmentioning

confidence: 99%

Correlation of vibrational intensity with fluorescence lifetimes in π conjugated polymers

O’Neill¹,

Lynch²,

McNamara³

et al. 2008

Polymer

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“…A further discussion of the adapted model and its observed trend is outside the scope of this paper and can be found elsewhere. 40 …”

Section: Resultsmentioning

confidence: 99%

Systematic Study of the Effects of Naphthalene and Anthracene Substitution on the Properties of PPV Derivative Conjugated Systems

Lynch¹,

O’Neill²,

Bradley³

et al. 2007

Macromolecules

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The systematic synthesis of poly(phenylvinylene) (PPV) derivatives by the Wittig-Horner reaction is reported. The phenyl units of the PPV structure are methodically substituted by naphthyl and anthryl units to form a homologous series of structures. The 2,6 attachment of the vinylene linkage on the anthryl ring provides novel structures that have not been reported before due to their synthetic inaccessibility. The introduction of naphthyl units results in a hypsochromatic shift in the absorption and emission spectra, while the introduction of anthryl units leads to a bathochromatic shift relative to the naphthalene structures. The observed structural variation of the spectroscopic properties is explained in terms of a combination of the increased conjugation of the substituent acene units and the decreased electronic contribution across the vinyl linkage.

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“…It was demonstrated that the systematic variation of the vibrational coupling along the backbone results in a systematic decrease in the non-radiative decay rates and thus an optimisation of the radiative yield. The systematic variation of the electron density of the vinylene bond of the polymer series by the introduction of naphthalene and anthracene moieties into the backbone [9,10,11] suggests that the photo-active stability can be similarly improved. This report presents a systematic study of the relative stabilities of polymers 1-6 ( Figure 1 The mechanisms and results of such degradation in conjugated polymers have been studied and presented at length in the literature [12].…”

Section: Introductionmentioning

confidence: 99%

Kinetic studies of the photo-degradation of poly(arylene vinylenes)

O’Neill¹,

Lynch²,

McGoldrick

et al. 2012

Journal of Luminescence

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This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting galley proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. AbstractThe kinetics of the degradation of a homologous series of Poly phenylene vinylenes in which the phenylene units of the PPV structure are systematically substituted by naphthyl and anthyrl units is presented. Degradation is monitored according to the decay of the long wavelength absorption maximum upon illumination with UV radiation. Compared to Toluene solution, the photo-degradation is seen to be accelerated in Chloroform solution. All decays are fitted with first order kinetics. It is found that all substitutions improve the stability of the vinylene polymers against decay.In particular the highly electro-negative naphthyl group serves to drastically increase the stability due to electron depletion across the vinyl bond. The decay rate is shown to correlate well with the variation of the electronic properties of the backbone and with the reduction of vinylene bond strength as measured using Raman spectroscopy.

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Spectroscopic Characterization of Novel Polycyclic Aromatic Polymers

Cited by 8 publications

References 22 publications

Correlation of vibrational intensity with fluorescence lifetimes in π conjugated polymers

Correlation of vibrational intensity with fluorescence lifetimes in π conjugated polymers

Systematic Study of the Effects of Naphthalene and Anthracene Substitution on the Properties of PPV Derivative Conjugated Systems

Kinetic studies of the photo-degradation of poly(arylene vinylenes)

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