Optical Nonlinearities in One-Dimensional-Conjugated Polymer Crystals

Sauteret, C.; Hermann, J. P.; Frey, R.; Pradère, F.; Ducuing, J.; Baughman, Ray H.; Chance, R. R.

doi:10.1103/physrevlett.36.956

Cited by 630 publications

(150 citation statements)

References 13 publications

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“…Such welldefined behavior is well-established and is the basis for our understanding of linear conjugated systems. 2,[19][20][21][22] It is clear, however, that both the short chain limit and the rate of decrease with increasing chain limit differ significantly with monomeric structure and the degree of coupling between the monomeric units. The differences in the long chain limit of the phenyl versus the acenes series mirrors the differences in band gaps of cis versus trans polyacetylene 7 and zigzag versus armchair singlewalled carbon nanotubes.…”

Section: Resultsmentioning

confidence: 99%

Structure−Property Relationships for Electron−Vibrational Coupling in Conjugated Organic Oligomeric Systems

O’Neill¹,

Byrne²

2005

J. Phys. Chem. B

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A series of π-conjugated oligomers containing one to six monomer units were studied by absorption and photoluminescence spectroscopy. As is common for these systems, a linear relationship between the positioning of the lowest-energy absorption and the highest-energy photoluminescence maxima plotted versus inverse conjugation length is observed, in good agreement with a simple nearly free electron model, one of the earliest descriptions of the properties of one-dimensional organic molecules. It was observed that the Stokes shift and therefore Huang-Rhys factor also exhibit a well-defined relationship with increasing conjugation length, implying a correlation between the electron-vibrational coupling and chain length. This correlation is further examined using Raman spectroscopy, whereby the integrated relative Raman scattering is seen to behave superlinearly with chain length. The Stokes shift and the Raman activity are also well-correlated in these systems. There is a clear indication that the vibrational activity and thus nonradiative decay processes are controllable through molecular structure.

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Section: Resultsmentioning

confidence: 99%

Structure−Property Relationships for Electron−Vibrational Coupling in Conjugated Organic Oligomeric Systems

O’Neill¹,

Byrne²

2005

J. Phys. Chem. B

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“…Equation (15) gives a reasonable result. An enlargement of yg } due to conjugated double bonds was discussed in [18][19][20][21]. Here we need the conjugated double bonds only to bring the S x absorption band to the visible region between co 1 and co 3 .…”

Section: Discussionmentioning

confidence: 99%

Third-order nonlinear susceptibilities of dye solutions determined by third-harmonic generation

Leupacher

Penzkofer

1985

Appl. Phys. B

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Abstract. The third-order nonlinear susceptibilities x { xxxx ( -^ w i> w i> &>i) versus concentration are determined for rhodamine 6G, fuchsin, and methylene blue in methanol. Third-harmonic generation of a modelocked Nd-glass laser is applied. The real and imaginary part of the nonlinear susceptibility are measured. A resonance enhancement due to absorption bands is observed. Here we determine the dependence of third-order nonlinear susceptibilities xx 3 xxx ( -^3; co l9 co u co x ) on dye concentration for rhodamine 6G, fuchsin and methylene blue in methanol. The efficiency of conversion of picosecond light pulses of a mode-locked Ndglass laser to the third harmonic is measured. The nonlinear susceptibilities are deduced by comparison with calculations [7]. The absorption coefficients and refractive indices entering the calculations are separately measured [8,9]. The nonlinear susceptibilities comprise contributions from the solvent and the solute. The complex solute hyperpolarizabilities are determined and compared with the real solvent hyperpolarizability. The resonance enhancement is analyzed.

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“…Since molecular packing in crystals is determined by the intermolecular interactions between monomers, the selection of substituents attached to the butadiyne moiety is quite important in the preparation of PDAs. On the other hand, much research on the physical properties of PDAs, such as electrical, 3,4 chromic [5][6][7] and nonlinear optical (NLO) [8][9][10] properties, which originate from the p-conjugated backbone structure, have been undertaken. In particular, the third-order NLO properties of PDAs have attracted interest.…”

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confidence: 99%

Solid-state polymerization of conjugated hexayne derivatives with different end groups

Inayama

Tatewaki

Okada

2009

Polym J

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Three hexayne derivatives with different end groups-that is, 10,12,14,16,18,20-triacontahexayne-1,30-diol (1) and its diphenylurethane (2) and diphenylester (3)-were synthesized, and their solid-state polymerization behaviors were investigated. All three monomers were thermally polymerizable. Polymers from 1 and 2 showed an absorption maximum at about 730 nm, indicating that linear polydiacetylenes (PDAs) with octatetraynyl substituents were synthesized. However, broad absorption bands in the near-infrared region were only observed for 2 at 980 and 860 nm, indicating that regular polymerization occurred in 2 to give ladder-type PDA. On the other hand, a polymer from 3 showed a visible absorption increase but no clear absorption maximum. It was estimated that intermolecular hydrogen bonding between hexayne monomers helps to form polymerizable stacks in 1 and 2. In particular, urethane groups are more effective, and 2 showed the highest reactivity in this study with an ordered interlayer structure even after a two-step solid-state polymerization to give ladder-type PDA. Keywords: ladder polymer; polydiacetylene; solid-state polymerization; p-conjugated polymer Some butadiyne compounds are polymerized in the solid state by ultraviolet irradiation or by thermal treatment. This solid-state polymerization was clarified by Wegner 1 as a single-crystal-to-singlecrystal topochemical transition to yield polydiacetylene (PDA), which is classified as a one-dimensional p-conjugated polymer. Since the reaction is topochemically controlled, the reactivity of butadiyne monomers is greatly affected by their packing in crystals. 2 In fact, when the butadiyne monomers in crystals have a stacking distance d of about 5 Å between adjacent molecules in the array and an angle y of about 45 1 between the butadiyne rod and stacking axis, 1,4-addition polymerization occurs. Since molecular packing in crystals is determined by the intermolecular interactions between monomers, the selection of substituents attached to the butadiyne moiety is quite important in the preparation of PDAs. On the other hand, much research on the physical properties of PDAs, such as electrical, 3,4 chromic 5-7 and nonlinear optical (NLO) [8][9][10] properties, which originate from the p-conjugated backbone structure, have been undertaken. In particular, the third-order NLO properties of PDAs have attracted interest. To achieve larger NLO susceptibility (w (3) ) in PDA, it is necessary to increase the density of the p-conjugated polymer backbone and the p-electron number in a repeating unit. In this connection, we have synthesized ladder-type PDAs, in which two polymer backbones were introduced in a repeating unit. 11,12 In addition, several PDAs with p-conjugated substituents, such as aromatic rings and C-C multiple bonds, directly bound to the polymer backbone [13][14][15][16][17][18][19][20][21][22] have been synthesized to obtain PDAs with absorption maxima at longer wavelengths, resulting in larger w (3) -values. In particular, oligoyne derivatives with five...

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Optical Nonlinearities in One-Dimensional-Conjugated Polymer Crystals

Cited by 630 publications

References 13 publications

Structure−Property Relationships for Electron−Vibrational Coupling in Conjugated Organic Oligomeric Systems

Structure−Property Relationships for Electron−Vibrational Coupling in Conjugated Organic Oligomeric Systems

Third-order nonlinear susceptibilities of dye solutions determined by third-harmonic generation

Solid-state polymerization of conjugated hexayne derivatives with different end groups

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