# US 11,999,884 B2 · Thermally stable polythiol ligands with pendant solubilizing moieties

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- Number: US 11,999,884 B2
- Document ID: US11999884B2
- Status: Granted
- Kind: B2
- Application number: 17/487,148
- Filed: 2021-09-28
- Published: 2022-03-31
- Granted: 2024-06-04
- Earliest claimed: 2020-09-28
- Assignees: Shoei Chemical Inc.
- Applicants: Shoei Chemical Inc.
- Inventors: David Olmeijer; Ravisubhash Tangirala; Austin Smith
- Web page: https://patentgrep.com/patent/US11999884B2

## CPC

- C09K 11/025: {non-luminescent particle coatings or suspension media}
- C07C 319/18: by addition of thiols to unsaturated compounds
- C09K 11/565: {with zinc cadmium}
- C09K 11/7492: {Arsenides; Nitrides; Phosphides}
- C09K 11/883: {with zinc or cadmium}
- B82Y 20/00: Nanooptics, e.g. quantum optics or photonic crystals
- B82Y 40/00: Manufacture or treatment of nanostructures
- C07C 323/22: containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES

## Abstract

The present invention provides nanostructure compositions and methods of producing nanostructure compositions. The nanostructure compositions comprise a population of nanostructures comprising polythiol ligands with pendant moieties. The polythiol ligand with pendant moieties increase the solubility of the nanostructures in solvents and resins. The present invention also provides nanostructure films comprising the nanostructure compositions and methods of making nanostructure films using the nanostructure compositions.

## Claims

### Claim 1

A nanostructure composition comprising:
(a) a nanostructure; and
(b) polythiol ligands dispersed on the surface of the nanostructure, the polythiol ligands having the formula I:
wherein:
CM is a central moiety, wherein CM is selected from the group consisting of an alkane, a 1,3,5-triazine, a pentaerythritol, a 1,3,5-triazine-2,4,6-trione, a trimethylolpropane, and a (propane-2,2-diylbis(4,1-phenylene))bis(λ′-oxy);
X1 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X2 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X3 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X4 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X5 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X6 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
B is —CH2—CH2—C(═O)—O—, —CH2—C(CH3)2—C(═O)—O—, —CH2—CH(CH3)—C(═O)—NH—, —C(═O)—NH—, —CH2—CH2—, or —CH2—CH(OH)—CH2—O—;
X7 is a bond or C1-12 alkylene;
X8 is a bond, —O—, —C(═O)—O—, or —C(═O)—N—;
R1A and R1B independently are H or C1-20 alkyl;
R2 is C1-20 alkyl or C1-20 alkoxy;
a is 2 to 10;
b is 0 to 10;
c is 2 to 10;
d is 0 to 10;
e is 1 to 100; and
f is 0 to 100;
wherein a+b+c+d has a value within a range of 4 to 40.

### Claim 2 (depends on 1)

The nanostructure composition of claim 1, wherein the polythiol ligands have formula II:
wherein:
CM is a central moiety;
X1 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X2 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X3 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
B is —CH2—CH2—C(═O)—O—, —CH2—C(CH3)2—C(═O)—O—, —CH2—CH(CH3)—C(═O)—NH—, —C(═O)—NH—, —CH2—CH2—, or —CH2—CH(OH)—CH2—O—;
X7 is a bond or C1-12 alkylene;
X8 is a bond, —O—, —C(═O)—O—, or —C(═O)—N—;
R1A and R1B independently are H or C1-20 alkylene;
R2 is C1-20 alkylene or C1-20 alkoxy;
a is 2 to 10;
c is 2 to 10;
e is 1 to 100; and
f is 0 to 100;
wherein a +c ≥4 and ≤20.

### Claim 3 (depends on 1)

The nanostructure composition of claim 1, wherein the nanostructure comprises a core selected from the group consisting of InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnSSe, InAs, InGaAs, and InAsP.

### Claim 4 (depends on 1)

The nanostructure composition of claim 1, wherein the nanostructure comprises at least one shell.

### Claim 5 (depends on 1)

The nanostructure composition of claim 1, wherein X1, X2, and X3 are a bond.

### Claim 6 (depends on 1)

The nanostructure composition of claim 1, wherein X1 is —C(═O)—, X2 is a C1-10 alkylene, and X3 is a bond.

### Claim 7 (depends on 1)

The nanostructure composition of claim 1, wherein X1 is C2-10 heteroalkylene, X2 is —C(═O)—, and X3 is a C1-10 alkylene.

### Claim 8 (depends on 1)

The nanostructure composition of claim 1, wherein X1 is a substituted C2-10 heteroalkylene, X2 is a bond, and X3 is a bond.

### Claim 9 (depends on 1)

The nanostructure composition of claim 1, wherein B is —CH2—CH2—.

### Claim 10 (depends on 1)

The nanostructure composition of claim 1, wherein X7 is a C1-10 alkylene and X8 is —C(═O)—O—.

### Claim 11 (depends on 1)

The nanostructure composition of claim 1, wherein R1A is H, e is 1 to 100, a is 2, and c is 2.

### Claim 12 (depends on 1)

The nanostructure composition of claim 1, wherein the nanostructure composition is soluble in a solvent selected from the group consisting of water, methanol, ethanol, acetone, methyl ethyl ketone, isopropanol, n-propanol, acetonitrile, dimethyl sulfoxide, dimethyl formamide, ethylene glycol, diethylene glycol, benzonitrile, cyclohexane, chloroform, ethyl acetate, propylene glycol methyl acetate, and dichloromethane.

### Claim 13

A method of replacing a first ligand on a nanostructure with a second ligand comprising admixing a reaction mixture comprising a population of nanostructures having a first ligand non-covalently bound to the nanostructure and a second ligand which is a polythiol ligand, such that the second ligand displaces the first ligand and becomes non-covalently bound to the nanostructure, wherein the polythiol ligand has formula I:
wherein:
CM is a central moiety, wherein CM is selected from the group consisting of an alkane, a 1,3,5-triazine, a pentaerythritol, a 1,3,5-triazine-2,4,6-trione, a trimethylolpropane, and a (propane-2,2-diylbis(4,1-phenylene))bis(λ′-oxy);
X1 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X2 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X3 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X4 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X5 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X6 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
B is —CH2—CH2—C(═O)—O—, —CH2—C(CH3)2—C(═O)—O—, —CH2—CH(CH3)—C(═O)—NH—, —C(═O)—NH—, —CH2—CH2—, or —CH2—CH(OH)—CH2—O—;
X7 is a bond or C1-12 alkylene;
X8 is a bond, —O—, —C(═O)—O—, or —C(═O)—N—;
R1A and R1B independently are H or C1-20 alkyl;
R2 is C1-20 alkyl or C1-20 alkoxy;
a is 2 to 10;
b is 0 to 10;
c is 2 to 10;
d is 0 to 10;
e is 1 to 100; and
f is 0 to 100;
wherein a+b+c+d has a value within a range of 4 to 40.

### Claim 14 (depends on 13)

The method of claim 13, wherein the nanostructure comprises a core selected from the group consisting of InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnSSe, InAs, InGaAs, and InAsP.

### Claim 15

A nanostructure film layer comprising:
(a) a nanostructure;
(b) polythiol ligands dispersed on the surface of the nanostructure, the polythiol ligands having the formula I:
wherein:
CM is a central moiety, wherein CM is selected from the group consisting of an alkane, a 1,3,5-triazine, a pentaerythritol, a 1,3,5-triazine-2,4,6-trione, a trimethylolpropane, and a (propane-2,2-diylbis(4,1-phenylene))bis(λ′-oxy);
X1 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X2 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X3 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X4 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X5 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
X6 is a bond, —C(═O)—, a C1-10 alkylene, or a C2-10 heteroalkylene;
B is —CH2—CH2—C(═O)—O—, —CH2—C(CH3)2—C(═O)—O—, —CH2—CH(CH3)—C(═O)—NH—, —C(═O)—NH—, —CH2—CH2—, or —CH2—CH(OH)—CH2—O—;
X7 is a bond or C1-12 alkylene;
X8 is a bond, —O—, —C(═O)—O—, or —C(═O)—N—;
R1A and R1B independently are H or C1-20 alkyl;
R2 is C1-20 alkyl or C1-20 alkoxy;
a is 2 to 10;
b is 0 to 10;
c is 2 to 10;
d is 0 to 10;
e is 1 to 100; and
f is 0 to 100;
wherein a+b+c+has a value within a range of 4 to 40; and
(c) at least one organic resin.

### Claim 16 (depends on 15)

The nanostructure film layer of claim 15, wherein the nanostructure film layer displays a light conversion efficiency between about 20% and about 40%.