The Colors of Polydiacetylenes: a Commentary

Schott, M.

doi:10.1021/jp0638437

Cited by 140 publications

(198 citation statements)

References 52 publications

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“…This result is another indication of the role played by the side groups in governing the backbone conjugation and, as a consequence, in determining the PDA colour. [35,36] On the basis of the present data, it is evident that on silver colloids a highly delocalized polymer is formed, favoured by the compact organization of the chemisorbed monomers. The fact that we detect this form only in the AgNPs can be attributed to the higher affinity of carboxylic groups for Ag than for Au surfaces, [21] which leads to a close packing of the absorbed molecules.…”

Section: Resultsmentioning

confidence: 49%

Photopolymerization in water of diacetylenes chemisorbed onto noble metal nanoparticles: a spectroscopic study

Raimondo

Alloisio

Demartini

et al. 2009

J Raman Spectroscopy

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Gold and silver nanoparticles of different size, decorated by a diacetylenic monomer having a COOH anchor group, were prepared in aqueous dispersions. Topochemical polymerization of the colloidal suspensions was obtained by UV irradiation and studied by means of spectroscopic techniques (UV-visible absorption, IR and Raman spectroscopies). A variety of polymer phases were found in the case of silver nanohybrids. The main contribution for this investigation was supplied by the Raman spectra, which provide detailed information on the polymer forms and on the preferred conformation of the alkylic side chains.

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Section: Resultsmentioning

confidence: 49%

Photopolymerization in water of diacetylenes chemisorbed onto noble metal nanoparticles: a spectroscopic study

Raimondo

Alloisio

Demartini

et al. 2009

J Raman Spectroscopy

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show abstract

“…Similarly, electronic interaction between polymer chains belonging to different lamellae is always negligible. This does not mean that the 3D packing of the lamellae is irrelevant, since the conformation of side groups may affect the chain geometry, hence its electronic structure [48].…”

Section: Resultsmentioning

confidence: 99%

Structural study of two reactive diacetylenes

et al. 2007

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“…1 Disorder effects have commonly been investigated in matrix isolated materials, such as polyenes, where subtle interplays between molecular shape and electronic structure have been identified. [2][3][4][5] However, matrix isolation on its own is not sufficient to overcome disorder but merely helps to screen intermolecular effects. The intrinsic molecular properties themselves are accessible with single-molecule spectroscopy.…”

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confidence: 99%

How Chromophore Shape Determines the Spectroscopy of Phenylene−Vinylenes: Origin of Spectral Broadening in the Absence of Aggregation

et al. 2008

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Single oligo(phenylene-vinylene) molecules constitute model systems of chromophores in disordered conjugated polymers and can elucidate how the actual conformation of an individual chromophore, rather than that of an overall polymer chain, controls its photophysics. Single oligomers and polymer chains display the same range of spectral properties. Even heptamers support π-electron conjugation across ∼80°curvature, as revealed by the polarization anisotropy in excitation and supported by quantum chemical calculations. As the chain becomes more deformed, the spectral linewidth at low temperatures, often interpreted as a sign of aggregation, increases up to 30-fold due to a reduction in photophysical stability of the molecule and an increase in random spectral fluctuations. The conclusions aid the interpretation of results from single-chain Stark spectroscopy in which large static dipoles were only observed in the case of narrow transition lines. These narrow transitions originate from extended chromophores in which the dipoles induced by backbone substituents do not cancel out. Chromophores in conjugated polymers are often thought of as individual linear transition dipoles, the sum of which make up the polymer's optical properties. Our results demonstrate that, at least for phenylene-vinylenes, it is the actual shape of the individual chromophore rather than the overall chromophoric arrangement and form of the polymer chain that dominates the spectroscopic properties.Molecular-level engineering in plastic electronics requires a precise understanding of how a particular physical or chemical structure impacts on the physical properties of the material. Disorder effects on the ensemble level can often mask the subtle interplay between function and structure. Large macromolecules such as conjugated polymers are particularly prone to energetic disorder, which gives rise to substantial spectral broadening and is generally attributed to a "particle in a box"-like picture of varying chromophore lengths. 1 Disorder effects have commonly been investigated in matrix isolated materials, such as polyenes, where subtle interplays between molecular shape and electronic structure have been identified. 2-5 However, matrix isolation on its own is not sufficient to overcome disorder but merely helps to screen intermolecular effects. The intrinsic molecular properties themselves are accessible with single-molecule spectroscopy. Although this technique helps to overcome the ensemble limitations, a single polymer chain can still contain many chromophores. [6][7][8][9][10][11][12] Energy transfer between these chromophores can mask the true photophysics of the individual spectroscopic unit. Although polarization-resolved spectroscopy has yielded detailed insight into the conformation of the polymer chain, 7,8,11,[13][14][15] very little is known about the shape of the indiVidual chromophore. Because a physical bend can potentially interrupt the π-electron conjugation, the chromophore is generally thought to be linearly extended in space...

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The Colors of Polydiacetylenes: a Commentary

Cited by 140 publications

References 52 publications

Photopolymerization in water of diacetylenes chemisorbed onto noble metal nanoparticles: a spectroscopic study

Photopolymerization in water of diacetylenes chemisorbed onto noble metal nanoparticles: a spectroscopic study

Structural study of two reactive diacetylenes

How Chromophore Shape Determines the Spectroscopy of Phenylene−Vinylenes: Origin of Spectral Broadening in the Absence of Aggregation

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