Near-IR Two-Photon Photoinitiated Polymerization Using a Fluorone/Amine Initiating System

Belfield, Kevin D.; Ren, Xiaobin; Stryland, Eric W. Van; Hagan, David J.; Dubikovsky, V.; Miesak, E.

doi:10.1021/ja991990v

Cited by 191 publications

(126 citation statements)

References 12 publications

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“…The spatial confinement of excitation and the ability to excite molecules with half of the energy required for linear absorption can be employed in three-dimensional microfabrication [2,3], three-dimensional optical storage [4,5], two-photon fluorescence imaging [6][7][8], two-photon photodynamic cancer therapy [9,10] and optical power limiting [11,12]. Motivated by these applications, efforts to understand the relationship between molecular structure and 2PA, aiming to design compounds with larger 2PA cross-section, have been carried out, leading to design strategies for novel organic materials [13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

Two-photon absorption spectrum in diazoaromatic compounds

Boni¹,

Andrade²,

Yamaki

et al. 2008

Chemical Physics Letters

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Section: Introductionmentioning

confidence: 99%

Two-photon absorption spectrum in diazoaromatic compounds

Boni¹,

Andrade²,

Yamaki

et al. 2008

Chemical Physics Letters

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“…7,8 As these PIs have rather low cross sections (r TPA ) and therefore poor absorption behavior, 9 high excitation power and long exposure time, which often result in damage to the polymeric structures are usually required. Therefore, great efforts were made to improve the two-photon sensitivity.…”

mentioning

confidence: 99%

Synthesis and structure‐activity relationship of several aromatic ketone‐based two‐photon initiators

Siklos

Pucher

et al. 2011

J. Polym. Sci. A Polym. Chem.

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Several novel aromatic ketone-based two-photon initiators containing triple bonds and dialkylamino groups were synthesized and the structure-activity relationships were evaluated. Branched alkyl chains were used at the terminal donor groups to improve the solubility in the multifunctional monomers. Because of the long conjugation length and good coplanarity, the evaluated initiators showed large two-photon cross section values, while their fluorescence lifetimes and quantum yields strongly depend on the solvent polarity. All novel initiators exhibited high activity in terms of two-photon-induced microfabrication. This is especially true for fluorenone-based derivatives, which displayed much broader processing windows than well-known highly active initiators from the literature and commercially available initiators. While the new photoinitiators gave high reactivity in two-photoninduced photopolymerization at concentration as low as 0.1% wt, these compounds are surprisingly stable under one photon condition and nearly no photo initiation activity was found in classical photo DSC experiment.

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“…These techniques are realized by a two-photon induced polymerization with a single processing step. The efficient two-photon absorbers based on the bis-(styryl)benzene constructs bearing electron-donating moieties were synthesized and found to undergo a presumed two-photon induced electron transfer to the functional triacrylate monomer by Perry et al [3,8,9]. It was proposed that molecules having the general structural motif D-core-D are sufficiently electron rich, they could transfer an electron to the monomer to activate the polymerized reaction upon two-photon excitation.…”

Section: Introductionmentioning

confidence: 99%

Investigation of mechanism of photo induced polymerization excited by two-photon absorption

Hasegawa

Kawazu

et al. 2004

Sen-i Gakkaishi

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Three kinds of the two-photon chromophores are used to investigate the process of electron transfer between the initiator and the multifunctional acrylate monomer in two-photon-induced polymerization. Their molecular structures are simplified as D--d--D, D--D and D--a--D, where D is the strong donor terminal group, is a -conjugated core, d and a are the electron-donating and electron-accepting side group linked with the -conjugated core, respectively. We noticed that the emission of those chromophores is very sensitive to the solvent polarity. Additionally, the red-shift, structureless and long-lived emission was observed in the monomer. Correlated with quantum chemical calculation (MOPAC-PM5), we proposed a process of electron transfer in two-photon-induced polymerization (TPIP). Following the non-irradiation from the high excited state (S 2 ), intramolecular charge transfer (intra-CT) takes place from the terminal group to the core in the primary step, where intra-CT state is named as intra-exciplex. Then the rapid electron hopping from the ion radical core of the chromophore to the monomer was initiated. The electron transfer produces the ion radical pair, attributed to the photopolymerization. Therefore, the rate of two-photon-induced polymerization is determined by an equilibrium of electron transfer and back electron transfer between initiator and monomer to some extent in spite of the contribution of highly sensitivity in two-photon absorption to the number of the excited chromophore.

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Near-IR Two-Photon Photoinitiated Polymerization Using a Fluorone/Amine Initiating System

Cited by 191 publications

References 12 publications

Two-photon absorption spectrum in diazoaromatic compounds

Two-photon absorption spectrum in diazoaromatic compounds

Synthesis and structure‐activity relationship of several aromatic ketone‐based two‐photon initiators

Investigation of mechanism of photo induced polymerization excited by two-photon absorption

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