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

Matthew Dalton

Loon-Seng Tan

Ramamurthi Kannan

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.

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Bellbrook, OH, United States of America

Matthew Dalton