Synthesis of New Multifunctional Polymers inCorporating BIS-(Diphenylamino)Diphenylpolyene Moieties

Spangler, Charles W.; Faircloth, Tami J.; Elandaloussi, El Hadj; Reeves, Benjamin D.

doi:10.1557/proc-488-283

Cited by 12 publications

(6 citation statements)

References 7 publications

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“…However, the early development of TPA-based applications was slow chiefly because the available materials had relatively small two-photon cross-sections. Then, in the mid-to-late 1990s, the momentum for the research-and-development activities in this field was accelerated by the discoveries of several classes of organic chromophores with very high two-photon responses. ,, In the wake of these discoveries, significant advances have been made in the design and synthesis of two-photon absorbing materials with very large cross-section (σ 2 ‘) values . In the meantime, the isolation of biological macromolecules with very large two-photon absorptivities has also been claimed .…”

Section: Introductionmentioning

confidence: 99%

Toward Highly Active Two-Photon Absorbing Liquids. Synthesis and Characterization of 1,3,5-Triazine-Based Octupolar Molecules

Kannan

Lin³

et al. 2003

Chem. Mater.

219

115

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Three novel two-photon absorbing (TPA) chromophores with 1,3,5-triazine as the π-electron deficient core, dialkylfluorene as aromatic bridges, and diphenylamino groups as the electrondonating end-groups were prepared. Designated as AF-450 (2,4,6-tris[7-(diphenylamino)-9,9-didecylfluoren-2-yl]-1,3,5-triazine), AF-455 (2,4,6-tris[9,9-bis(3,7-dimethyloctyl)-7-(diphenylamino)-fluoren-2yl]-1,3,5-triazine), and AF-457 (2,4,6-tris[(7-(diphenylamino)-9,9-diprop-2-enylfluoren-2-yl]-1,3,5-triazine), their overall molecular structure and local symmetry (D 3h ) are similar to those of previously reported three-armed AF-350 (N,N,N-tris[4-{7-(2benzothiazolyl)-9,9-diethylfluoren-2-yl}phenyl]amine) and AF-380 (N,N,N,-tris[7-(2-benzothiazolyl)-9,9-diethylfluoren-2-yl]amine). Among the family of AFX chromophores previously reported by us, AF-450 possesses one of the largest effective TPA cross-sections (σ 2 ′ ) 39 500 × 10 -50 cm 4 -sec/photon-molecule, or 39 500 GM) as determined by nonlinear transmission method in the nanosecond regime at 800 nm. In contrast, AF-455, a mixture of stereoisomers with the same chemical formula as AF-450, is a glassy material that becomes fluid (molasses-like) upon heating at 70-80 °C and has noticeably smaller effective σ 2 ′ value (33 300 GM). AF-457 (σ 2 ′ ) 27 800 GM) with six allyl side groups was prepared as a precursor toward the synthesis of a TPA liquid. The intrinsic TPA cross-sections of these chromophores were also determined as a function of excitation wavelengths via a femtosecond white-light continuum generation and direct degenerate-TPA measurement technique. At the TPA peaks ∼779 nm, their σ 2 ′ values are 216, 214, and 199 GM ((15%) for AF-450, AF-455, and AF-457, in that order. They are in the same trend as the nanosecond values, albeit two orders of magnitude lower.

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Section: Introductionmentioning

confidence: 99%

Toward Highly Active Two-Photon Absorbing Liquids. Synthesis and Characterization of 1,3,5-Triazine-Based Octupolar Molecules

Kannan

Lin³

et al. 2003

Chem. Mater.

219

115

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“…In the mid-1990s, several new classes of chromophores exhibiting very large effective TPA cross-section (σ 2 ‘) values were reported from our laboratories and other groups . In conjunction with the increased availability of ultrafast high-intensity lasers, not only has the renewed interest sparked a flurry of activities in the preparation of novel dye molecules with enhanced σ 2 ‘ values, but also many previously conceived applications based on TPA process in photonics and biophotonics are now enabled by these new chromophores. It is important to recognize the following features of two-photon materials technology: (a) upconverted emission, whereby an incident light at lower frequency (energy) can be converted to an output light at higher frequency, for instance, IR to UV−vis upconversion; (b) deeper penetration of incident light; (c) highly localized excitation allowing for precision control of in situ photochemical events in the absorbing medium, thereby minimizing undesirable activities such as photodegradation or photobleaching; and (d) fluorescence, when properly manipulated, that allows for information feedback.…”

Section: Introductionmentioning

confidence: 99%

Diphenylaminofluorene-Based Two-Photon-Absorbing Chromophores with Various π-Electron Acceptors

Kannan¹,

He²,

Yuan³

et al. 2001

Chem. Mater.

272

189

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A new series of linear, asymmetrical diphenylaminofluorene-based chromophores (AFX) with various strong π-electron acceptors were synthesized and evaluated for two-photon absorptivity. These chromophores were studied to determine a suitable replacement for 2-(4-vinyl)pyridine, the π acceptor for our previously reported AFX series, which contains a photochemically and thermo-oxidatively unstable olefinic unit. In addition to the benzoyl group (AF-370), these π-electron acceptors include 2-benzothiazolyl (AF-240), 2-benzoxazolyl (AF-390), 2-(N-phenyl)benzimidazolyl (AF-386), and 2-(3,4-diphenyl)imidazolyl (AF-385) moieties (five-membered heterocycles) and the 2-quinoxalinyl (AF-260) group (six-membered heterocycle). From nanosecond nonlinear transmission measurements, these new chromophores have effective two-photon cross sections (σ2‘) at 800 nm, spanning from 3.87 × 10-48 cm4 s/(photon molecule) for AF-385 to 97.46 × 10-48 cm4 s/(photon molecule) for AF-240. Two of them, 2-benzothiazolyl-end-capped AF-240 and benzoyl-containing AF-370 [σ2‘ = 84.32 × 10-48 cm4 s/(photon molecule)] stand out as having relatively good, albeit lower, values of two-photon cross sections, as compared to that of previously reported N,N-diphenyl-7-[2-(4-pyridinyl)ethenyl]-9,9-didecyl-fluorene-2-amine, AF-50 [σ2‘ = 115.6 × 10-48 cm4 s/(photon molecule)]. However, we observed that AF-240 was more photochemically robust than AF-50 when their THF solutions were subjected to repetitive and prolonged exposure to nanosecond laser radiation. Finally, on the basis of our nanosecond TPA cross-section data (σ2‘/MW values), the general trend for π-electron accepting ability, i.e., ability to accept charge transferred from diphenylamine appears to be as follows: 2-(4-vinyl)pyridine > 2-benzothiazolyl > benzoyl > 2-(N-phenylbenzimidazolyl > 2-quinoxalinyl > 2-benzoxazolyl > 2-(4,5-diphenyl)imidazoyl.

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“…Over the past five years we have studied the syntheses and photonic properties of series of bis-(diphenylamino)-substituted diphenylpolyenes and PPV oligomers 1,2 . Upon oxidation in solution with SbCl 5 , these polyenes and oligomers form exceptionally stable polaron-like radical cations and/or bipolaron-like dications.…”

Section: Introductionmentioning

confidence: 99%

Photonic Properties of Dendrons and Dendrimers Incorporating Bis-(Diphenylphosphino)Diphenylpolyenes

1999

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Substituent effects are quite important in fine tuning the photonic properties of conjugated molecules. In designing new chromophores, electron-donating or withdrawing substituents affect the electron distribution in the conjugation sequence, and previous studies to establish structureproperty relationships have noted that when second row elements replace first row elements in the structure (e.g. S for O in donor groups), large enhancements of both the second and third order optical nonlinearity are observed. However, along with the observed enhancement of the nonlinearity, a red-shift in the absorption spectra occurs, often with peak broadening and tailing. This absorptivity-nonlinearity trade-off has been a constant concern in proposing organic materials for electro-optic device applications. In this presentation we will review our recent activity in designing new chromophores wherein P replaces N in donor groups and dendrimer building blocks, and the consequences and opportunities resulting from the observed large blue shifts in the spectra.

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Synthesis of New Multifunctional Polymers inCorporating BIS-(Diphenylamino)Diphenylpolyene Moieties

Cited by 12 publications

References 7 publications

Toward Highly Active Two-Photon Absorbing Liquids. Synthesis and Characterization of 1,3,5-Triazine-Based Octupolar Molecules

Toward Highly Active Two-Photon Absorbing Liquids. Synthesis and Characterization of 1,3,5-Triazine-Based Octupolar Molecules

Diphenylaminofluorene-Based Two-Photon-Absorbing Chromophores with Various π-Electron Acceptors

Photonic Properties of Dendrons and Dendrimers Incorporating Bis-(Diphenylphosphino)Diphenylpolyenes

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