DERIVATIVES OF NANOMATERIALS AND RELATED DEVICES AND METHODS
A functionalized trimetallic nitride endohedral fullerene based material can be represented according to the formula: A3-nXnN@Cm (R)o, wherein: where A and X are one or a combination of the following metal atoms: Sc, Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Tm, Lu; (n=0-3); N is nitrogen; Cm is a fullerene and m=about 60-about 200; and R is an organic, inorganic, or organometallic species. Related compositions, devices and methods are also described.
1 . A functionalized trimetallic nitride endohedral fullerene composition comprising:
A 3-n X n N@C m (R) o ), wherein;
A and X are metal atoms: Sc, Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Tm or Lu;
n=0-3;
N is nitrogen;
C m is a fullerene and m=about 60-about 200;
R is an organic species, an inorganic species or an organometallic species; and
1≦o≦m.
2 . The composition of claim 1 , wherein R possesses characteristics that enhance interactions between the trimetallic nitride endohedral fullerene and a donor material.
3 . The composition of claim 1 , wherein R is and organic species, the organic species comprising at least one of: PCBV, wherein PCB stands for phenyl (P), C m+1 (C), butyric acid (B) or any other organic acid, and V is methyl (M), butyl (B), hexyl (H), or octyl (O); PCBW, wherein W is a modification to the side chains to induce more favorable interactions between the trimetallic nitride endohedral fullerene and a donor material; and ZCBW, wherein Z is a modification of the phenyl group which enhances the interactions between the trimetallic nitride endohedral fullerene and a donor material.
4 . The composition of claim 3 , wherein W comprises an amide which contains linear or branched alkyls groups and/or saturated or aromatic moieties.
5 . The composition of claim 3 , wherein W comprises an ester which contains linear or branched alkyl groups and or saturated or aromatic moieties.
6 . The composition of claim 4 , wherein the aromatic moieties comprise a phenyl, a thiophene, or a pyrrole, or a combination of aromatic groups.
7 . The composition of claim 1 , wherein R is linked to A 3-n X n N@C m by one or more of: a single bond to a carbon on the surface of the C m cage; addends connected to two-carbons on the surface of the carbon cage; a 1,2-,1,3-, and/or 1,4-addition; an unsaturated bond; an dative or ionic bond; or any supramolecular interaction.
8 . The composition of claim 1 , wherein R comprises a Diels-Alder (DA) adduct attached to the C m carbon cage.
9 . The composition of claim 1 , wherein R possesses characteristics that improve the solubility of the composition in a polymer.
10 . The composition of claim 1 , wherein the composition comprises:
Sc 3 N@C 80 -PCBM; Sc 3 N@C 80 -PCBB; N-(4-methoxyphenyl)ethyl Pyrrolido-Sc 3 N@C 80 ; methyl 3-benzoate DA-Sc 3 N@C 80 ; Sc 3 N@C 80 -PCBEH; Lu 3 N@C 80 -PCBM; Lu 3 N@C 80 -PCBB; Lu 3 N@C 80 -PCBO; Lu 3 N@C 80 -PCBH; Lu 3 N@C 80 -iPr-malonate; Lu 3 N@C 80 -PCBEH; Lu 3 N@C 80 -PCBMP; Lu 3 N@C 80 -PCBBP; methyl 3-benzoate DA-Lu 3 N@C 80 ; 3-phenyl DA-Lu 3 N@C 80 benzoate; Lu 3 N@C 80 -PCB(EH)amide; Lu 3 N@C 80 -PCB(BP)amide; Y 3 N@C 80 -PCBH; or Y 3 N@C 80 -PCBEH.
11 . The composition of claim 1 , wherein R imparts A 3-n X n N@C m with the ability to intimately interact with a donor polymer at a bulk heterojunction.
12 . The composition of claim 11 , wherein R comprises a saturated alkyl with branched or un-branched groups, un-saturated alkyl functionalities, aromatic moieties, polar entities, and/or metals.
13 . The composition of claim 1 , wherein R comprises at least one chromophore.
14 . The composition of claim 13 , wherein the chromophore possesses characteristics that improve the ability of the composition to harvest the solar spectrum.
15 . The composition of claim 13 , wherein the chromophore comprises porphyrin, a phthalocyanine, or an inorganic/organic complex capable of absorbing light in any region of the solar spectrum.
16 . The composition of claim 1 , wherein R possesses characteristics that facilitate interactions between a solvent system, a polymer, and the composition.
17 . The composition of claim 1 , wherein R possesses characteristics that facilitate two-photon absorption by the composition.
18 . The composition of claim 1 , wherein R possesses characteristics that enables the composition to become capable of multiple exciton generation.
19 . The composition of claim 1 , wherein the composition exhibits an irreversible reductive behavior.
20 . The composition of claim 1 , wherein the composition exhibits a reversible reductive behavior.
21 . A functionalized trimetallic nitride endohedral fullerene composition comprising:
A n X q Y r N@C m (R) o , wherein;
A, X and Y are metal atoms: Sc, Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Tm or Lu;
n=0-3;
q=0-3;
r=0-3;
n+q+r=3;
N is nitrogen;
C m is a fullerene and m=about 60-about 200;
R is an organic species, an inorganic species or an organometallic species; and
1≦o≦m.
22 . The composition of claim 21 , wherein R possesses characteristics that enhance interactions between the trimetallic nitride endohedral fullerene and a donor material.
23 . The composition of claim 21 , wherein R possesses characteristics that improve the solubility of the composition in a polymer.
24 . The composition of claim 21 , wherein R imparts A 3-n X n N@C m with the ability to intimately interact with a donor polymer at a bulk heterojunction.
25 . The composition of claim 21 , wherein R comprises at least one chromophore.
26 . The composition of claim 25 , wherein the chromophore possesses characteristics that improve the ability of the composition to harvest the solar spectrum.
27 . The composition of claim 21 , wherein R possesses characteristics that facilitate interactions between a solvent system, a polymer, and the composition.
28 . The composition of claim 21 , wherein R possesses characteristics that facilitate two photon absorption by the composition.
29 . The composition of claim 21 , wherein R possesses characteristics that enables the composition to become capable of multiple exciton generation.
30 . The composition of claim 21 , wherein the composition exhibits an irreversible reductive behavior.
31 . The composition of claim 21 , wherein the composition exhibits a reversible reductive behavior.
32 . A material comprising the composition of claim 1 .
33 . The material of claim 32 , wherein the material comprises a conductive polymer.
34 . The material of claim 33 , wherein the conductive polymer comprises poly 3-hexyl thiophene.
35 . A photovoltaic device comprising the material of claim 32 .
36 . The device of claim 35 , wherein the device comprises a bulk heterojunction type device.
37 . A photovoltaic device, the device comprising an active layer, the active formed at least in part from the composition of claim 1 .
38 . The device of claim 37 , wherein the active layer further comprises a conductive polymer.
39 . A method of functionalizing a trimetallic nitride endohedral fullerene, the method comprising: reacting the trimetallic nitride endohedral fullerene with a paraformaldehyde (HCOH), and an amino acid such as Q-N Q′-glycine, wherein N is the nitrogen of the glycine, Q is a substituent on the nitrogen, and Q′ could be hydrogen or a second substituent on the alpha carbon of the amino acid.
40 . The method of claim 39 , wherein Q comprises one or more of: an alkyl and an aryl.
41 . The method of claim 40 , wherein the alkyl and aryl comprise a carbon chain longer than three carbons.
42 . The method of claim 39 , wherein the reaction is performed using a ratio of 1:10:50 of the trimetallic nitride endohedral fullerene to the Q-N glycine to the paraformaldehyde.
43 . The method of claim 39 , wherein the reaction occurs in 10 minutes or less.
44 . A method of functionalizing a trimetallic nitride endohedral fullerene, the method comprising: reacting the trimetallic nitride endohedral fullerene with a hydrazone and sodium methoxide.
45 . The method of claim 44 , wherein the reaction is performed using a ratio of 1:10:10 of the trimetallic nitride endohedral fullerene to the hydrazone to the sodium methoxide.
46 . The method of claim 45 , wherein the reaction occurs at a temperature of at least about 120° C.
47 . The method of claim 46 , wherein the reaction occurs over period of time of 20 minutes or less.
48 . A method of functionalizing a trimetallic nitride endohedral fullerene, the method comprising: reacting the trimetallic nitride endohedral fullerene with a sultine in a o-dichlorobenzene solvent.
49 . The method of claim 48 , wherein the reaction is performed using a ratio of 1:25:30 of the trimetallic nitride endohedral fullerene to sultine.
50 . The method of claim 48 , wherein the reaction is carried out for a period of time of 15 minutes or less.
51 . The method of claim 48 , wherein a substituted o-xylene is included in the reaction.
52 . The method of claim 51 , wherein the substituted o-xylene comprises 3,4-dimethyl benzoic acid.
53 . A material comprising a fullerene, an endohedral metal fullerene, or a trimetallic nitride endohedral fullerene, the material comprising an energetically highest observed LUMO with reduction potentials of <about −1.20 V to about −1.54 V vs. ferrocene/ferrocenium.
54 . The material of claim 53 , wherein the material is functionalized.
55 . A material comprising a fullerene, an endohedral metal fullerene, or a trimetallic nitride endohedral fullerene, the material comprising an energetically lowest observed HOMO with reduction potentials of about +0.07 V to about 0.0 V vs. ferrocene/ferrocenium.
56 . The material of claim 55 , wherein the material is functionalized.
57 . A p-type or donor substance formed from the material of claim 55 .