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US 7,459,106 B2Granted
Materials, methods, and uses for photochemical generation of acids and/or radical species
AssigneeArizona Board of Regents on Behalf of the University of Arizona
InventorsSeth Marder, Joseph Perry, Wenhui Zhou, Stephen M. Kuebler, J. Kevin Cammack
Life of this patent
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Abstract
The present invention provides compounds and compositions, which include: at least one chromophore having strong simultaneous two-photon or multi-photon absorptivity; at least one acid- or radical-generator in close proximity to the chromophore; such that the single- or multi-photon excitation of the chromophore results in the generation of an acid and/or redical that is capable of activating chemistry; and such that compositions of matter based on the componds and compositions of the invention can be photo-patterned by one- or multiphoton excitation.
Claims24
A compound or composition, comprising:
- at least one chromophore having a simultaneous two-photon or multi-photon absorptivity;
- and
- at least one photoacid or radical generator in close proximity to said chromophore;
- wherein said chomophore has a two-photon absorption cross-section of >50×10−50 cm4 s/photon.
- (1) wherein the generator is a sulfonium group has of formula —(CH2)γ—(C6H4)δ—SRarRa6,
- wherein Ra5 and Ra6 are each independently alkyl, aryl, or monomer groups, and
- wherein γ=0 to 25, and δ=0 to 5;
- (2) wherein the generator is a selenonium group of the formula —(CH2)γ—(C6H4)δ—SeRa5Ra6,
- wherein Ra5 and Ra6 are each independently alkyl, aryl, or monomer groups, and
- wherein γ=0 to 25, and δ=0 to 5;
- or
- (3) wherein the generator is an iodonium group of the formula —(CH2)γ—(C6H4)δ—IRa7,
- wherein Ra7 is alkyl, aryl, or monomer group, and
- wherein γ=0 to 25, and δ=0 to 5.
11 more elements
A composition which has the structure:
- wherein X═S, Se, I, O, N and n=0, 1, 2, 3, 4, or 5,
- wherein Ar1 and Ar2 are each independently a 5-membered heteroaromatic ring;
- a 6-membered aromatic ring;
- or a 6-membered heteroaromatic ring,
- wherein each of Ar1 and Ar2 are optionally independently substituted with one or more H, alkyl group, alkoxy group, or aryl group, which groups may be optionally independently substituted with one or more sulfonium, selenonium, or iodonium groups;
- other acid- or radical-generating species;
- or monomer or pre-polymer groups,
- wherein R1, R2, R3, and R4 are each independently alkyl or aryl groups, which groups may be optionally independently substituted one or more sulfonium, selenoniumn, or iodonium groups;
- other acid- or radical-generating species;
- or monomer or pre-polymer groups,
- wherein Y is an anion selected from the group consisting of F−, Cl−, Br−, I−, CN−, SO42−, PO43−, CH3CO2−, CF3SO3−, NO2−, NO3−, BF4−, PF6−, SbF6−, AsF6−, SbCl4−, ClO331, ClO4−, and B(aryl)4−, where aryl is an aryl group containing 25 or fewer carbon atoms that may be optionally substituted with one or more alkyl groups, aryl groups or halogens,
- wherein z is an integer equal to the charge of the chromophore portion of the compound,
- wherein p is an integer equal to the charge on the anion, and
- wherein q and Q are integers such that the relationship zQ=pq is satisfied.
11 more elements
A composition which has the structure:
- wherein X is I, S, Se or O, n=0, 1, 2, 3, 4, or 5, and n′=0, 1, 2, 3, 4 or 5,
- wherein Ar1 and Ar2 are each independently a 5-membered heteroaromatic ring;
- a 6-membered aromatic ring;
- or a 6-membered heteroaromatic ring,
- wherein Ar3 is a 5-membered heteroaromatic ring;
- a 6-membered aromatic ring;
- or a 6-membered heteroaromatic ring,
- wherein each of Ar1 and Ar2 are optionally independently substituted with one or more H, alkyl group, alkoxy group, or aryl group, which groups may be optionally independently substituted with one or more sulfonium, selenonium, or iodonium groups;
- other acid- or radical-generating species;
- or monomer or pre-polymer groups,
- wherein Ar3 is optionally substituted with one or more H, acceptor group, alkyl group, alkoxy group, aryl group, which groups may be optionally independently substituted with one or more sulfonium, selenonium, or iodonium groups;
- other acid- or radical-generating species;
- or monomer or pre-polymer groups,
- wherein R1 and R2 are each independently alkyl group, or aryl group, which groups may be optionally independently substituted with one or more sulfonium, selenonium, or iodonium groups;
- other acid- or radical-generating species;
- or monomer or pre-polymer groups,
- wherein Y is an anion selected from the group consisting of F−, Cl−, Br−, I−, CN−, SO42−, PO43−, CH3CO2−, CF3SO3−, NO2−, NO3−, BF4−, PF6−, SbF6−, AsF6−, SbCl4−, ClO3−, ClO4−;
- and B(aryl)4−;
- where aryl is an aryl group containing 25 or fewer carbon atoms that may be optionally substituted with one or more alkyl groups, aryl groups or halogens,
- wherein z is an integer equal to the charge of the chromophore portion of the compound,
- wherein p is an integer equal to the charge on the anion, and
- wherein q and Q are integers such that the relationship zQ=pq is satisfied.
19 more elements
A composition which has the structure:
- wherein X is N, n=0, 1, 2, 3, 4, or 5, n′=0, 1, 2, 3, 4 or 5 and n′″=0, 1, 2, 3, 4, or 5,
- wherein Ar1 and Ar2 are each independently a 5-membered heteroaromatic ring;
- a 6-membered aromatic ring;
- or a 6-membered heteroaromatic ring,
- wherein Ar3 is a 5-membered heteroaromatic ring;
- a 6-membered aromatic ring;
- or a 6-membered heteroaromatic ring,
- wherein each of Ar1 and Ar2 are optionally independently substituted with one or more H, alkyl group, alkoxy group, aryl group, which groups may be optionally independently substituted with one or more sulfonium, selenonium, or iodonium groups;
- other acid- or radical-generating species;
- or monomer or pre-polymer groups,
- wherein Ar3 is optionally substituted with one or more H, acceptor group, alkyl group, alkoxy group, aryl group, which groups may be optionally independently substituted with one or more sulfonium, selenonium, or iodonium groups;
- other acid- or radical-generating species;
- or monomer or pre-polymer groups,
- wherein R1, R2, R3, and R4 are each independently H, alkyl group, aryl group, which groups may be optionally independently substituted with one or more sulfonium, selenonium, or iodonium groups;
- other acid- or radical-generating species;
- or monomer or pre-polymer groups,
- wherein at least one of Ar1, Ar2, Ar3, R1, R2, R3, or R4 is substituted with one or more sulfonium, selenonium, or iodonium groups, or other acid- or radical generating groups,
- wherein Y is an anion selected from the group consisting of F−, Cl−, Br−, I−, CN−, SO42−, PO43−, CH3CO2−, CF3SO3−, NO2−, NO3−, BF4−, PF6−, SbF6−, AsF6−, SbCl4−, ClO3−, ClO4−, and B(aryl)4−, where aryl is an aryl group containing 25 or fewer carbon atoms that may be optionally substituted with one or more alkyl groups, aryl groups or halogens,
- wherein z is an integer equal to the charge of the chromophore portion of the compound,
- wherein p is an integer equal to the charge on the anion, and
- wherein q and Q are integers such that the relationship zQ=pq is satisfied.
18 more elements
A compound or composition, which has the structure:
- wherein X is N, n=0, 1, 2, 3, 4 or 5, n′=0, 1, 2, 3, 4, or 5 and n′″=0, 1, 2, 3, 4, or 5,
- wherein Ar1 and Ar2 are each independently a 5-membered heteroaromatic ring;
- a 6-membered aromatic ring;
- or a 6-membered heteroaromatic ring,
- wherein Ar3 is a 5-membered heteroaromatic ring;
- a 6-membered aromatic ring;
- or a 6-membered heteroaromatic ring,
- wherein each of Ar1 and Ar2 are optionally independently substituted with one or more H, alkyl, alkoxy, aryl, thioalkoxy, thioaryloxy, selenoalkoxy, or selenoaryloxy groups, which groups may be optionally independently substituted with monomer or pre-polymer groups,
- wherein Ar3 is optionally independently substituted with one or more H, acceptor, alkyl, alkoxy, aryl, thioalkoxy, thioaryloxy selenoalkoxy, or selenoaryloxy groups, which groups may be optionally independently substituted with monomer or pre-polymer groups,
- wherein R1, R2, R3, and R4 are each independently H, alkyl, or aryl groups, which groups may be optionally independently substituted with one or more thioalkoxy, thioaryloxy selenoalkoxy, selenoaryloxy or groups, and
- wherein at least one of Ar1, Ar2, Ar3, R1, R2, R3, or R4 is substituted with one or more thioalkoxy, thioaryloxy selenoalkoxy, selenoaryloxy groups.
8 more elements
A composition of a form selected from the group consisting of:
- wherein R is methyl or benzyl, and
- wherein X is F−, Cl−, Br−, I−, CN−, SO42−, PO43−, CH3CO2−, CF3SO3−, NO2−, NO3−, BF4−, PF6−, SbF6−, AsF6−, SbCl4−, ClO3−, ClO4−, or B(aryl)4−, where aryl is an aryl group containing 25 or fewer carbon atoms that may be optionally substituted with one or more alkyl groups, aryl groups or halogens.
Dependencies are inferred from the claim text.