Two-photon or higher-order absorbing optical materials and methods of use

A method for preparing a compound in an electronically excited state, comprising the steps of:

• a) exposing a compound having the formula D1-Π-D2 to radiation of a wavelength within a multiphoton absorption peak of said compound, wherein D1 and D2 are electron donor groups;
• and Π comprises a bridge of π-conjugated bonds connecting D1 and D2;
• and
• b) converting said compound to a multi-photon electronically excited state upon simultaneous absorption of at least two photons of said radiation by said compound, wherein the sum of the energies of all of said absorbed photons is greater than or equal to the transition energy from a ground state of said compound to said multi-photon excited state and wherein the energy of each absorbed photon is less than the transition energy between said ground state and the lowest single-photon excited state of said compound and is less than the transition energy between said multi-photon excited state and said ground state, wherein said compound is further defined by a formula
• where Da is selected from the group consisting of N, O, S, and P;
• where Db is selected from the group consisting of N, O, S, and P;
• m, n, o are integers such that 1≦m≦10, 0≦n≦10, and 0≦o≦10;
• and
• where:
• X and Z are independently selected from the group consisting of CRk═CRl, O, S, and N—Rm;
• Ra, Rb, Rc, Rd are independently selected from the group consisting of H, a linear or branched alkyl group with up to 25 carbons, —(CH2CH2O)α—(CH2)βORa1, —(CH2CH2O)α—(CH2)βNRa2Ra3, —(CH2CH2O)α—(CH2)βCONRa2Ra3, —(CH2CH2O)α—(CH2)βCN, —(CH2CH2O)α—(CH2)βCl, —(CH2CH2O)α—(CH2)βBr, —(CH2CH2O)α—(CH2)βI, —(CH2CH2O)α—(CH2)β-Phenyl, a group of aromatic rings having up to 20 carbons in the aromatic ring framework, fused aromatic rings, vinyl, allyl, 4-styryl, acroyl, methacroyl, acrylonitrile, isocyanate, isothiocyanate, epoxides, strained ring olefins, (—CH2)δSiCl3, (—CH2)δSi(OCH2CH3)3, and (—CH2)δSi(OCH3)3, where 0<δ<25;
• wherein one of Ra and Rb is not present when Da is O or S, and wherein one of Rc and Rd is not present when Db is O or S;
• Re, Rf, Ri, Rj, Rk, and Rl are independently selected from the group consisting of H, a linear or branched alkyl group with up to 25 carbons, —(CH2CH2O)α—(CH2)βORb1, —(CH2CH2O)α—(CH2)βNRb2Rb3, —(CH2CH2O)α—(CH2)βCONRb2Rb3, —(CH2CH2O)α—(CH2)βCN, —(CH2CH2O)α—(CH2)βCl, —(CH2CH2O)α—(CH2)βBr, —(CH2CH2O)α—(CH2)βI, —(CH2CH2O)α—(CH2)β-Phenyl, a group of aromatic rings having up to 20 carbons in the aromatic framework, fused aromatic rings, CHO, CN, NO2, Br, Cl, I, phenyl, an acceptor group having more than two carbon atoms, a functional group obtained by reaction with an amino acid, NRe1Re2, and ORe3;
• Rm is selected from the group consisting of H, a linear or branched alkyl group with up to 25 carbons, —(CH2CH2O)α—(CH2)βORb1, —(CH2CH2O)α—(CH2)βNRb2Rb3, —(CH2CH2O)α—(CH2)βCONRb2Rb3, —(CH2CH2O)α—(CH2)βCN, —(CH2CH2O)α—(CH2)βCl, —(CH2CH2O)α—(CH2)βBr, —(CH2CH2O)α—(CH2)βI, —(CH2CH2O)α—(CH2)β-Phenyl, a group of aromatic rings having up to 20 carbons in the aromatic framework, fused aromatic rings, phenyl, an acceptor group having more than two carbon atoms, and a functional group obtained by reaction with an amino acid;
• where 0<α<10 and 1<β<25;
• Ra1, Ra2, and Ra3 are independently selected from the group consisting of H, a linear or branched alkyl group with up to 25 carbons, and a functional group obtained by reaction with:
• an amino acid, a polypeptide, adenine, guanine, tyrosine, cytosine, uracil, biotin, ferrocene, ruthenocene, cyanuric chloride, or methacryloyl chloride;
• Rb1, Rb2, and Rb3 are each independently a functional group obtained by reaction with:
• an amino acid, a polypeptide, adenine, guanine, tyrosine, cytosine, uracil, biotin, ferrocene, ruthenocene, cyanuric chloride, or methacryloyl chloride;
• Re1, Re2, Re3 are independently selected from the group consisting of H, a linear or branched alkyl group with up to 25 carbons, —(CH2CH2O)α—(CH2)βORg1, —(CH2CH2O)α—(CH2)βNRg2Rg3, —(CH2CH2O)α—(CH2)βCONRg2Rg3, —(CH2CH2O)α—(CH2)βCN, —(CH2CH2O)α—(CH2)βCl, —(CH2CH2O)α—(CH2)βBr, —(CH2CH2O)α—(CH2)βI, —(CH2CH2O)α—(CH2)β-Phenyl, aryl groups, fused aromatic rings, vinyl, allyl, 4-styryl, acroyl, methacroyl, acrylonitrile, isocyanate, isothiocyanate, epoxides, strained ring olefins, (—CH2)δSiCl3, (—CH2)δSi(OCH2CH3)3, and (—CH2)δSi(OCH3)3, where 0<δ<25;
• Rg1, Rg2, and Rg3 are independently selected from the group consisting of H, a linear or branched alkyl group with up to 25 carbons, and a functional group obtained by reaction with:
• an amino acid, a polypeptide, adenine, guanine, tyrosine, cytosine, uracil, biotin, ferrocene, ruthenocene, cyanuric chloride, or methacryloyl chloride.

A method for preparing a compound in an electronically excited state, comprising the steps of:

• a) exposing a compound having the formula D1-Π-D2 to radiation of a wavelength within a multiphoton absorption peak of said compound, wherein D1 and D2 are electron donor groups;
• and Π comprises a bridge of π-conjugated bonds connecting D1 and D2;
• and
• b) converting said compound to a multi-photon electronically excited state upon simultaneous absorption of at least two photons of said radiation by said compound, wherein the sum of the energies of all of said absorbed photons is greater than or equal to the transition energy from a ground state of said compound to said multi-photon excited state and wherein the energy of each absorbed photon is less than the transition energy between said ground state and the lowest single-photon excited state of said compound and is less than the transition energy between said multi-photon excited state and said ground state, wherein said compound is further defined by a formula
• where Da is selected from the group consisting of N, O, S, and P;
• where Db is selected from the group consisting of N, O, S, and P;
• m, n, o are integers such that 1≦m≦10, 0≦n≦10, and 0≦o≦10;
• and
• where:
• X and Z are independently selected from the group consisting of CRk═CRl, O, S, and N—Rm;
• Ra, Rb, Rc, Rd are independently selected from the group consisting of H, a linear or branched alkyl group with up to 25 carbons, —(CH2CH2O)α—(CH2)βORa1, —(CH2CH2O)α—(CH2)βNRa2Ra3, —(CH2CH2O)α—(CH2)βCONRa2Ra3, —(CH2CH2O)α—(CH2)βCN, —(CH2CH2O)α—(CH2)βCl, —(CH2CH2O)α—(CH2)βBr, —(CH2CH2O)α—(CH2)βI, —(CH2CH2O)α—(CH2)β-Phenyl, a group of aromatic rings having up to 20 carbons in the aromatic ring framework, fused aromatic rings, vinyl, allyl, 4-styryl, acroyl, methacroyl, acrylonitrile, isocyanate, isothiocyanate, epoxides, strained ring olefins, (—CH2)δSiCl3, (—CH2)δSi(OCH2CH3)3, and (—CH2)δSi(OCH3)3, where 0<δ<25;
• wherein one of Ra and Rb is not present when Da is O or S, and wherein one of Rc and Rd is not present when Db is O or S;
• Re, Rf, Ri, Rj, Rk, Rl and Rm are independently selected from the group consisting of, H, a linear or branched alkyl group with up to 25 carbons, —(CH2CH2O)α—(CH2)βORb1, —(CH2CH2O)α—(CH2)βNRb2Rb3, —(CH2CH2O)α—(CH2)βCONRb2Rb3, —(CH2CH2O)α—(CH2)βCN, —(CH2CH2O)α—(CH2)βCl, —(CH2CH2O)α—(CH2)βBr, —(CH2CH2O)α—(CH2)βI, —(CH2CH2O)α—(CH2)β-Phenyl, a group of aromatic rings having up to 20 carbons in the aromatic framework, fused aromatic rings, CHO, CN, NO2, Br, Cl, I, phenyl, an acceptor group containing more than two carbon atoms, a functional group obtained by reaction with an amino acid, NRe1Re2, and ORe3;
• where 0<α<10 and 1<β<25;
• Ra1, Ra2, and Ra3 are independently selected from the group consisting of H, a linear or branched alkyl group with up to 25 carbons, and a functional group obtained by reaction with:
• an amino acid, a polypeptide, adenine, guanine, tyrosine, cytosine, uracil, biotin, ferrocene, ruthenocene, cyanuric chloride, or methacryloyl chloride;
• Rb1, Rb2, and Rb3 are each independently a functional group obtained by reaction with:
• an amino acid, a polypeptide, adenine, guanine, tyrosine, cytosine, uracil, biotin, ferrocene, ruthenocene, cyanuric chloride, or methacryloyl chloride;
• Re1, Re2, Re3 are independently selected from the group consisting of H, a linear or branched alkyl group with up to 25 carbons, —(CH2CH2O)α—(CH2)βORg1, —(CH2CH2O)α—(CH2)βNRg2Rg3, —(CH2CH2O)α—(CH2)βCONRg2Rg3, —(CH2CH2O)α—(CH2)βCN, —(CH2CH2O)α—(CH2)βCl, —(CH2CH2O)α—(CH2)βBr, —(CH2CH2O)α—(CH2)βI, —(CH2CH2O)α—(CH2)β-Phenyl, aryl groups, fused aromatic rings, vinyl, allyl, 4-styryl, acroyl, methacroyl, acrylonitrile, isocyanate, isothiocyanate, epoxides, strained ring olefins, (—CH2)δSiCl3, (—CH2)δSi(OCH2CH3)3, and (—CH2)δSi(OCH3)3, where 0<δ<25;
• Rg1, Rg2, and Rg3 are independently selected from the group consisting of H, a linear or branched alkyl group with up to 25 carbons, and a functional group obtained by reaction with:
• an amino acid, a polypeptide, adenine, guanine, tyrosine, cytosine, uracil, biotin, ferrocene, ruthenocene, cyanuric chloride, or methacryloyl chloride.

A method for preparing a compound in an electronically excited state, comprising the steps of:

• a) exposing a compound having the formula D1-Π-D2 to radiation, wherein D1 and D2 are electron donor groups;
• and Π comprises a bridge of π-conjugated bonds connecting D1 and D2;
• and
• b) converting said compound to a multi-photon electronically excited state upon simultaneous absorption of at least two photons of said radiation by said compound, wherein the sum of the energies of all of said absorbed photons is greater than or equal to the transition energy from a ground state of said compound to said multi-photon excited state and wherein the energy of each absorbed photon is less than the transition energy between said ground state and the lowest single-photon excited state of said compound and is less than the transition energy between said multi-photon excited state and said ground state, wherein said compound is selected from the group consisting of
• and mixtures thereof, where R═(CH2)11CH3.