United States of America As Represented by the Secretary of the Air Force

Other

The Mead Corporation

Ramamurthi Kannan

Loon-Seng Tan

Matthew Dalton

Bruce A Reinhardt

Richard A Vaia

Jim C Spain

Lawrence L Brott

Stephen J Clarson

Lloyd J Nadeau

By Jason Reinhardt, Administrator

By Erin Reinhardt, Administrator

Bruce A Reinhardt, Deceased

Steven L Yeager

A two-photon absorbing (TPA) compound is provided, along with a method of making same. The TPA compound has a general structural formula: where A is an acceptor moiety that is connected to m number of diarylaminofluorene arms (m=1-3); in each diarylaminofluorene arms, R is selected from linear or branched alkyl chains having a general formula CH, where n is in a range from 2 to 25; where R, R, and Rare independently selected from H or C-Calkyls; where Ris selected from C-Calkyls; and wherein Rthrough Rare independently selected from H, alkoxyls, alkyls, or aryls. A may be benzothiazol-2-yl, benzo[1,2-d:4,5-d']bisthiazole-2,6-diyl, thiazolo[5,4-d]thiazole-2,5-diyl-, 1,3,5-triazine-2,4,6-triyl, 1,3,5-triazine-2,4,6-triyl, benzo[1,2-d:3,4-d&#x2032;:5,6-d&#x2033;]tristhiazole-2,5,8-triyl-, or dithieno[3,2-b:2&#x2032;,3&#x2032;-d]thiophene-2,6-diyl-.

Two-photon absorbing compounds and methods of making same

Diphenylamine-benzobisthiazole-diphenylamine monomers having two-photon absorption cross-sections and high solubility in organic solvents are provided. Also provided are the corresponding organo-soluble, wholly conjugated and two-photon absorbing benzobisthiazole-triarylamine polymers.

Two-photon absorbing polymers based on triarylamine-benzobisthiazole-triarylamine quadrupolar-structure motif

A method of synthesizing a two-photon active tris(diarylamino-9,9-di(R)fluorenyl)-1,3,5-triazine compound having the structure: where Y is hydrogen, a thermally self-polymerizable acrylic, or a methacrylic group; R is an alkyl group of the formula &#x2014;CH, wherein the subscript m ranges from 1 to 6, or an alkylether group of the formula &#x2014;(CHCHO)Me, wherein the subscript p ranges from 1 to 5; R' is an alkyl group; and the R&#x2032;&#x2014;(OY)groups are attached to the phenyl rings of the triarylamine moiety either in a para position or a meta position and the subscript x ranges from 1 to 3. The compound may be synthesized by (a) synthesizing a diarylamine intermediate, (b) synthesizing a brominated 1,3,5-triazine intermediate as a three-arm core structure, and (c) forming the two-photon active tris(diarylamino-9,9-di(R)fluorenyl)-1,3,5-triazine compound by covalently joining the diarylamine and each arm of the three-arm core structure and removing the acetone protecting groups. The diarylamine intermediate may be synthesized by protecting tris-1,1,1-(hydroxymethyl)ethane, via a ketal formation with acetone, as an acetonide derivative; furnishing bromophenoxy-methyltrimethyl-1,3-dioxane from the acetonide derivative; and arylating aniline with the bromophenoxy-methyltrimethyl-1,3-dioxane.

Synthesis of two-photon absorbing polyhydroxy diphenylamino-dialkylfluorene-1,3,5-triazine molecules

Two-photon absorbing (2PA), cross-linked polyurethanes were prepared from bis(isocyanato) monomers, tris(isocyanato) monomers or a mixture thereof, in conjunction with novel polyol molecules with donor-acceptor octupolar geometry, whose generic structure is comprised of an electron-accepting 1,3,5-triazine hub with three spokes constituted by electron-donating triarylalkylamine end-groups, which are polyfunctionalized with thermally reactive alcohol functions. The resulting neat glassy or rubbery solids are applicable in a wide range of linear and nonlinear optical applications.

Two-photon absorbing cross-linked polyurethanes containing diphenylamino-dialkylfluorene-1,3,5-triazine units

Provided are novel polyimides, poly(amide-imides) and polyamides, which are generated from new two photon diamino-monomers of the formula: wherein para or meta X&#x2014;CH&#x2014;O&#x2014; and X&#x2550;NH; and CHis either a straight or branched alkyl chain, and wherein n is an integer from 1 to 20.

Aromatic polyimides, polyamides and poly(amide-imide) containing diarylaminofluorene-benzothiazole moieties as two-photon active units

Provided are novel 2PA-active monomers of the formula: wherein Y&#x2550;H, acrylic or methacrylic moiety; R is a linear or branched alkyl group, &#x2014;CH, where m=1-6 or an alkylether group, &#x2014;(CHCHO)Me, where p=1-5. The number of R'&#x2014;(OH)groups, attached to the phenyl rings of the triarylamine moiety either in a para or a meta position, could be 3 or 6 per molecule, or mixtures of molecules containing 3, 4, 5, 6 in various ratios and wherein x=1, 2, or 3. R&#x2032; is a linear or branched alkyl group such as &#x2014;CH, where m=1-6, i.e. linear &#x2014;(CH), where m=2-6, or branched alkyl group such as &#x2014;CHCH(R&#x2033;)&#x2014;, where R&#x2033;&#x2550;&#x2014;(CH)CH, where l=2-6.

Two-photon absorbing polyhydroxy diphenylamino-dialkylfluorene-1,3,5-triazine  molecules

Two-photon absorbing arylamine-endcapped and dialkylfluorene-bridged benzobisthiazole-based compounds are provided. These two-photon absorbing benzobisthiazole-based compounds show high solubility in nonpolar hydrocarbon solvents (oleophilicity) and high two-photon properties, especially in the nanosecond domain of pulse-laser excitation.

Two-photon absorbing arylamine-endcapped and dialkylfluorene-bridged benzobisthiazole compounds with high oleophilicity

Two-photon absorbing (2PA), cross-linked polyurethanes were prepared from bis(isocyanato) monomers, tris(isocyanato) monomers or a mixture of bis(isocyanato) and tris(isocyanato) monomers, in conjunction with a novel polyol molecules with donor-acceptor octupolar geometry, whose generic structure is comprised of an electron-accepting 1,3,5-triazine hub with three spokes constituted by electron-donating triarylalkylamine end-groups, which are polyfunctionalized with thermally reactive alcohol functions. The resulting neat glassy or rubbery solids are applicable in a wide range of linear & nonlinear optical applications.

Two-photon absorbing cross-linked polyurethanes containing delphenylamino-dialkyffluorene-1,3,5-triazine units

Provided are new 2PA chromophores of the formula: wherein X=para- or meta-NO; para- or meta-NH; and CHis either a straight or branched alkyl chain, and n is an integer from 1-20.

Two-photon absorbing diphenylaminofluorene-benzothiazole bis(aminophenoxy) monomers

A novel o-aminophenol-carboxylic AB-monomer with the following chemical structure: for synthesizing new rigid-rod polybenzobisazoles was prepared from the corresponding nitrobenzothiazolecarboxylic acid via an enzymatic process.

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Provided are new two-photon absorbing chromophores of the formula: wherein R is an alkyl group having 1 to 20 carbon atoms and Q is OH, OMe, propargyloxy-(O&#x2014;CH&#x2014;C&#x2261;CH), methylpropargyloxy-(O&#x2014;CH&#x2014;C&#x2261;C&#x2014;CH), allyloxy-(O&#x2014;CH&#x2014;C&#x2550;CH),1-methyl-allyloxy(O&#x2014;CH&#x2014;CH&#x2550;CHCH) and 3-methyl-allyloxy (O&#x2014;CH(CH)&#x2014;CH&#x2550;CH).

Thermally cross-linkable two-photon chromophores

Provided are chromophores of the formula: wherein R is an alkyl group having 1 to 20 carbon atoms, and Q is &#x2014;(CH)&#x2014;Br, and wherein n has a value of 2&#x2013;6.

Two-photon absorbing chromophores containing polymerizable olefinic groups

Provided are new TPA chromophores of the formula:wherein R is an alkyl group having 1 to 20 carbon atoms and Q is &#x2014;CH, &#x2014;CH&#x2014;CH, or &#x2014;CH.

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Cincinnati, OH, United States of America

Ramamurthi Kannan