Correlation of vibrational intensity with fluorescence lifetimes in π conjugated polymers

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

doi:10.1016/j.polymer.2008.07.035

Cited by 12 publications

(10 citation statements)

References 29 publications

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“…Well-defined relationships relating the variation in conjugation across the π back-bone to vibrational coherence have served to establish empirical relationships describing the variation of the fluorescence yield with Stokes shift, integrated Raman intensity and electronic band-gap [19,20,21,22].…”

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

Influence of Auxiliary Ligands on the Photophysical Characteristics of a Series of Ruthenium(II)–Polypyridyl Complexes

O’Neill¹,

Perdisatt²,

O’Connor³

2012

J. Phys. Chem. A

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A series of ruthenium−polypyridyl complexes were studied using UV/vis absorption and luminescence spectroscopy as well as luminescence lifetime determination by time-correlated single photon counting (TCSPC). The complexes were characterized with regard to the variation in the electronic band gap as a result of the sequential variation of the auxiliary ligand 2,2′-bipyridine (bpy), 1,10phenanthroline (phen), and 2,2′-biquinoline (biq) ligands while the main ligand remained constant for three different main ligand types. Luminescence yields were calculated and correlated with structural and electronic variation. It was found that both the absorption and emission characteristics could be tailored through the systematic variation of the reduction potential of the individual auxiliary ligand. This was shown to be the case regardless of the functional group at the end of the main ligand. Stokes shift and Raman spectroscopy were employed as a means to gauge the effect of ligand change on the conjugation and vibrational characteristics of the complexes. Luminescence yield and lifetimes were also shown to be well-defined with regards to systematic structure variations. The well-defined trends established elucidate the effect which variation of auxiliary ligands has on the electronic and excited state characteristics of the ruthenium−polypyridyl systems. These well-defined relationships can potentially be extended to optimize luminescence yield and lifetimes and therefore suitability of such compounds for the application in for example photodynamic therapy.

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Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

Influence of Auxiliary Ligands on the Photophysical Characteristics of a Series of Ruthenium(II)–Polypyridyl Complexes

O’Neill¹,

Perdisatt²,

O’Connor³

2012

J. Phys. Chem. A

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“…When the excited electrons relax mainly through radiative decay processes, increased QYs will be observed. If the contribution of non‐radiative processes is significant, the opposite will be expected . Using the relationship between the fluorescence lifetime ( τ F ) and QY ( Φ F ), k nr = (1 − Φ F )/ τ F , the radiative and non‐radiative decay rates of PPEs and PPBs were obtained before and after complexation (Table , Fig.…”

Section: Resultsmentioning

confidence: 99%

Controlled ionic complexation of positively charged phenylene‐based conjugated polymers by modulated backbone structures

Manandhar

Vokatá

Lee

et al. 2018

Polymer International

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Understanding the role of the polymer backbone structure on the aggregation of conjugated polymers in an aqueous environment is of prime interest as the physical, photophysical and biophysical properties required for many applications are closely related to the nature of aggregation structures. We report unique and ordered aggregation behaviours of four positively charged conjugated polymers, which differ in backbone chemical structure and connectivity, upon complexation with a linear polyanion hyaluronic acid. Opposite signals of induced circular dichroism were observed from achiral poly(phenyleneethynylene) (PPE) and flexible linker containing poly(phenylenebutadiynylene) (PPB) with the same side chain structure, implying the formation of highly ordered ionic complexes. The intrinsic difference in the interpolymer interaction between PPE and PPB is probably the contributing factor for different aggregation structures upon complexation with hyaluronic acid. The structure–property relationship can be useful to design and fabricate highly ordered macromolecular materials exhibiting unique electrical, photophysical or biophysical properties. © 2018 Society of Chemical Industry

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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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Correlation of vibrational intensity with fluorescence lifetimes in π conjugated polymers

Cited by 12 publications

References 29 publications

Influence of Auxiliary Ligands on the Photophysical Characteristics of a Series of Ruthenium(II)–Polypyridyl Complexes

Influence of Auxiliary Ligands on the Photophysical Characteristics of a Series of Ruthenium(II)–Polypyridyl Complexes

Controlled ionic complexation of positively charged phenylene‐based conjugated polymers by modulated backbone structures

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

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