US 7,235,194 B2 · Two-photon or higher-order absorbing optical materials for generation of reactive species

Abstract

Disclosed are highly efficient multiphoton absorbing compounds and methods of their use. The compounds generally include a bridge of pi-conjugated bonds connecting electron donating groups or electron accepting groups. The bridge may be substituted with a variety of substituents as well. Solubility, lipophilicity, absorption maxima and other characteristics of the compounds may be tailored by changing the electron donating groups or electron accepting groups, the substituents attached to or the length of the pi-conjugated bridge. Numerous photophysical and photochemical methods are enabled by converting these compounds to electronically excited states upon simultaneous absorption of at least two photons of radiation. The compounds have large two-photon or higher-order absorptivities such that upon absorption, one or more Lewis acidic species, Lewis basic species, radical species or ionic species are formed.

A chromophore selected from the group consisting of

where
Da and Db are independently selected from the group consisting of N, O, S, and P;
Lg is selected from the group consisting of
(i) —OR1, —NR1R2, —N+R1R2R3, —PR1R2, —P+R1R2R3, —SR1, —S+R1R2, Cl, Br, I, —I+R1, where R1, R2, and R3 are independently selected from the group consisting of
(a) H;
(b) a linear or branched alkyl group with up to 25 carbons;
(c) —(CH2CH2O)α—(CH2)βORa1, —(CH2CH2O)α—(CH2)βNRa2Ra3, —(CH2CH2O)α—(CH2)βCONRa2Ra3, —(CH2CH2O)60 —(CH2)βCN, —(CH2CH2O)β—(CH2)βCl, —(CH2CH2O)α—(CH2)βBr, —(CH2CH2O)α—(CH2)62 I, —(CH2CH2O)60 (CH2) 62 -phenyl, where 0≦α≦10, 1 ≦β≦25 and Ral, Ra2, and Ra3 are independently selected from the group consisting of H and a linear or branched alkyl group with up to 25 carbons;
(d) an aryl group;
(e) a fused aromatic ring;
(f) a polymerizable functionality;
(g) —F, —Br, —Cl, —I, phenyl;
(h) —NRe1, Re2, —ORe3, —SRe4, where Re1, Re2, Re3, Re4 are independently selected from the group consisting of
(1) H;
(2) a linear or branched alkyl group with up to 25 carbons;
(3) phenyl;
and
(4) a polymerizable functionality;
(ii) a functional group derived essentially from an amino acid selected from the group consisting of alanine;
valine;
leucine;
isoleucine;
proline;
tryptophan;
phenylalanine;
methionine;
glycine;
serine;
threonine;
tyrosine;
cysteine;
glutamine;
asparagine;
lysine;
arginine;
histidine;
aspartic acid;
glutamic acid;
(iii) a polypeptide;
(iv) adenine, guanine, tyrosine, cytosine, uracil, biotin, ferrocene, ruthenocene, cyanuric chloride and derivatives thereof;
and
(v) methacryloyl chloride;
m, n, o and p are independently selected from the range of integers greater than or equal to zero and less than or equal to ten;
U, V, X, and Y are independently selected from the group consisting of CRk′═CR1′, O, S, and N—Rm′, where Rk′, R1′, and Rm′are defined below;
Ra, Rb, Rc and Rd are independently selected from the group consisting of
(i) —H;
(ii) a linear or branched alkyl group with up to 25 carbons;
(iii) —(CH2CH2O)α—(CH2)βORa1;
—(CH2CH2O)α—(CH2)βNRa2Ra3;
—(CH2CH2O)α—(CH2)βCONRa2Ra3;
—(CH2CH2O)β—(CH2)βCN;
—(CH2CH2O)α—(CH2)βCl;
—(CH2CH2O) α—(CH2)βBr;
—(CH2CH2O)α—(CH2)βI;
—(CH2CH2O)α—(CH2)β—Phenyl, where 0≦α≦10 and 1≦β≦25 and Ra1, Ra2, and Ra3 are independently selected from the group consisting of H and a linear or branched alkyl group with up to 25 carbons;
(iv) an aryl group;
(v) a fused aromatic ring;
and
(vi) a polymerizable functionality;
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, Rg, Rn, Ri, RJ, Rk, Rk′, R1, R1′, Rm′, Rp, Rq, Rr, Rs, Rt, Ru, Rv, R1, R2, and R3 are independently selected from the group consisting of
(i) H;
(ii) a linear or branched alkyl group with up to 25 carbons;
(iii) —(CH2CH2O)α—(CH2)βORa1, —(CH2CH2O)α—(CH2) βNRa2Ra3, —(CH2CH2O)α—(CH2)62 CONRa2Ra3, —(CH2CH2O)α—(CH2)βCN, —(CH2CH2O)α—(CH2)βCl, —(CH2CH2O)α—(CH2)βBr, —(CH2CH2O) α—(CH2)βI, _(CH2CH2O)α—(CH2)β-Phenyl, where 0≦α≦10 and 1≦β≦25 and Ra1, Ra2, and Ra3 are independently selected from the group consisting of H and a linear or branched alkyl group with up to 25 carbons;
(iv) an aryl group;
(v) a fused aromatic ring;
(vi) a polymerizable functionality;
(vii) —F, —Br, —Cl, —I, phenyl;
(viii) —NRe1Re2, —ORe3, and —SRe4, where Rel, Re2, Re3, Re4 are independently selected from the group consisting of
(a) H;
(b) a linear or branched alkyl group with up to 25 carbons;
(c) phenyl;
and
(d) a polymerizable functionality
or an electrically neutral salt thereof.

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Two-photon or higher-order absorbing optical materials for generation of reactive species

Life of this patent

Two-photon or higher-order absorbing optical materials for generation of reactive species

Life of this patent

Abstract

Claims28