Quantum dots with donor-acceptor ligands

Abstract

The present invention provides nanostructure compositions and methods for making the nanostructure compositions. The nanostructure compositions comprise a population of nanostructures that comprise donor-acceptor ligands. The present invention also provides nanostructure films comprising the nanostructure compositions, and methods for making nanostructure films using the nanostructure compositions.

Description

[Technical Field]

[0001] Background of the Invention FIELD OF THE INVENTION The present invention provides a nanostructure composition and a method for making the nanostructure composition. The nanostructure composition comprises a population of nanostructures that comprise donor-acceptor ligands. The present invention also provides a nanostructure film comprising the nanostructure composition, and a method for making a nanostructure film using the nanostructure composition. [Background technology]

[0002] Background of the Invention

[0002] Quantum dots linked by long-chain aliphatic acids exhibit poor conductivity due to the insulating properties of the ligands. In inorganic semiconductors, the electron effective mass is much smaller than the vacancy effective mass, resulting in high electron mobility, so that ligand stripping or exchange for smaller ligands often results in n-type conductivity with electrons as the primary charge carriers.

[0003] Two parameters govern the power consumption of organic light-emitting diodes (OLEDs): the device stack and the quantum yield of light emission from the light-emitting materials. The driving voltage of an OLED is highly sensitive to the thickness of different layers in the device, as well as the charge transport capabilities and energy levels of the materials. By minimizing the energy gap between adjacent layers and facilitating charge injection from the electrodes, hole and electron injection and transport can be achieved at lower operating voltages. The second parameter, photoluminescence quantum yield, is limited in fluorescent materials because only singlet excitons are available for light emission; therefore, the internal quantum efficiency (IQE) of fluorescent OLEDs is limited to 25% (Bui, T.-T., Beilsten J. Org. Chem. 14:282-308 (2018)). Conversely, intersystem crossing allows phosphorescent OLEDs to achieve a theoretical internal quantum efficiency of 100%, allowing phosphorescent materials to harvest singlet and triplet excitons for light emission.

[0004]

[0004] Materials in the light-emitting layer of OLEDs should match the energy levels for charge injection and possess bipolar properties, possessing both electron-transporting and hole-transporting properties to enable the formation of both stable cation and anion radicals. Therefore, there is growing interest in discovering materials with bipolar transport properties for OLEDs. Because charge-carrier transport in small molecules is a chain of redox processes between neutral molecules and the corresponding radical ions, electron-donating and electron-withdrawing moieties have the potential to transport holes and electrons, respectively. Therefore, one strategy to achieve bipolar transport in organic molecules is to incorporate both electron-donating (donor) and electron-withdrawing (acceptor) building blocks within the same molecule (Duan, L., et al., Advanced Materials 23:1137-1144 (2011)).

[0005]

[0005] Bipolar host molecules composed of carbazole, pyridoindole, and dibenzothiophene have been found to be effective for blue thermally activated delayed fluorescence (TADF)-based OLEDs (Kang, JS, et al., Journal of Materials Chemistry C 4:4512-4520 (2016)). These molecules have been shown to have low driving voltages and high external quantum efficiencies (EQEs), which are attributed to the well-controlled bipolarity of the hosts, which leads to good charge balance in the emissive layer.

[0006]

[0006] Thermally activated delayed fluorescence (TADF) emitters thermally rearrange from the triplet state to the singlet state through reverse intersystem crossing, resulting in an increase in emission intensity. TADF emitters behave by collecting both singlet and triplet excitons for radiative transition, except that in OLEDs, emission occurs from the singlet state rather than the triplet state (the opposite of what is observed in metal complexes), and the triplet-triplet annihilation typically observed in phosphorescent OLEDs can be dramatically reduced. Thus, TADF offers the high performance and fluorescent material stability of triplet emitters while eliminating the triplet-triplet annihilation and poor device stability observed in phosphorescent OLEDs and the poor IQE observed in fluorescent OLEDs.

[0007] TADF emitters are composed of strong donors and acceptors that localize the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) on the donor and acceptor moieties, respectively. The spatial separation of the HOMO and LUMO lowers the singlet energy of TADF emitters while leaving the triplet energy largely unaffected (Im, Y., et al., Chemistry of Materials 29:1946-1963 (2017)). Conversely, weak donors and acceptors induce less significant HOMO and LUMO localization, resulting in a small reduction in the singlet energy. Therefore, strong donor and acceptor moieties have been found to be better than weak donor and acceptor moieties for reducing the emission energy of TADF emitters.

[0008] There is a need to prepare nanostructure compositions and / or resin mixtures that, when used to fabricate nanostructure films, have improved voltage stability and improved photoluminescence quantum yield of the quantum dot layer. Summary of the Invention [Means for solving the problem]

[0009] Summary of the Invention

[0009] The present disclosure provides: (a) at least one population of nanostructures; (b) at least one donor-acceptor ligand; wherein the donor-acceptor ligand comprises at least one terminal functional group, and the at least one terminal functional group is attached to a surface of the nanostructure.

[0010] In some embodiments, the nanostructure composition comprises 1 to 5 populations of nanostructures, hi some embodiments, the nanostructure composition comprises 2 populations of nanostructures.

[0011] In some embodiments, the nanostructures of the nanostructure composition comprise a core selected from the group consisting of InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnTe, ZnSeTe, ZnS, ZnSSe, InAs, InGaAs, and InAsP, hi some embodiments, the nanostructures of the nanostructure composition comprise a core of InP.

[0012] In some embodiments, the nanostructures of the nanostructure composition comprise at least one shell.

[0013] In some embodiments, the nanostructures of the nanostructure composition comprise a ZnS shell.

[0014] In some embodiments, the nanostructures of the nanostructure composition comprise a ZnS shell and a ZnSe shell.

[0015] In some embodiments, the nanostructures of the nanostructure composition comprise an InP core, a ZnS shell, and a ZnSe shell.

[0016] In some embodiments, the donor-acceptor ligand of the nanostructure composition has Formula I or Formula II: D d -A a -FG f (I) or A a -D d -FG f (II) and In the above formula, FG is -OH, -SH, -NH2, -CO2H, -P(O)(OH)2, -P(O)OH, or -SO3H; D is a donor moiety comprising a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; A is an acceptor moiety that independently for each occurrence comprises a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer of 1 to 4.

[0017] In some embodiments, FG in the donor-acceptor ligand is —CO 2 H.

[0018] In some embodiments, A in the donor-acceptor ligand is: (i) A compound of formula V: [ka] (Wherein, A1 to A6 independently contain C or N, and at least one of A1 to A6 is N; R1, R2, and R3 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18haloaryl); or (ii) A compound of formula IX: [ka] (In the formula, A 11 ~A 14 independently contains C or N, and A 11 ~A 14 at least one of is N; X1 is O, S, or NR 12 and; R 10 and R 11 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 12 But hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (iii) A compound of formula X: [ka] (In the formula, A 15 ~A 22 independently comprises C or N; X2 is O or S; R 13 , R 14 , and R 15 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (iv) A compound of formula XI: [ka] (In the formula, A 23 ~A 34 independently comprises C or N; R 16 , R 17 , and R 18 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (v) A compound of formula XII: [ka] (In the formula, A 35 ~A 38 independently comprises C or N; X3 is O, S, or NR 21 and; R 19 and R 20 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 21 is hydrogen, C 1~10 Alkyl, C 6~18aryl, or heteroaryl; or (vi) Compound of formula XIII: [ka] (In the formula, A 39 and A 40 independently comprises C or N; X4 to X7 are independently C, O, S, or NR 23 and at least one of X4 to X7 is NR 23 and; R 22 is hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 23 But hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (vii) Compound of formula XIV: [ka] (In the formula, A 41 ~A 53 independently contain C or N); or (viii) Compound of formula XV: [ka] wherein X8 is C(O) or S(O)2; X9 is CR 26 R 27 , C(O), or S(O)2; R 24 and R 25 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 26 and R 27 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (ix) Compound of formula XVI: [ka] (In the formula, A 54 ~A 61 independently comprises C or N; X 10 is CR 30 R 31 , S, O, or S(O)2; R 28 and R 29 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 30 and R 31 are independently hydrogen, C 1~10 Alkyl, C 2~10Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (x) A compound of formula XVII: [ka] (In the formula, R 32 But -SO2-(C 6~18 aryl), -CN, -C(O)-(C 6~18 aryl), -C(O)-(C 6~18 aryl)-C(O)-(C 6~18 aryl), -SO2-(C 6~18 aryl)-SO2-(C 6~18 aryl), or -B-(C 6~18 aryl)2; R 33 But hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 34 But hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl) is an acceptor site containing a radical of

[0019] In some embodiments, A in the donor-acceptor ligand is an acceptor moiety selected from the group consisting of radicals of the following compounds: [ka] [ka] [ka] [ka] [ka]

[0020] In some embodiments, A in the donor-acceptor ligand has formula V: [ka] and an acceptor moiety that is a radical of a compound having In the above formula, A1 to A6 independently contain C or N, and at least one of A1 to A6 is N; R1, R2, and R3 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0021] In some embodiments, at least one of R 1 , R 2 , or R 3 in the compound of formula V is —CN, methyl, phenyl, or pyridine.

[0022] In some embodiments, A in the donor-acceptor ligand has formula VI: [ka] and an acceptor moiety that is a radical of a compound having In the above formula, R4 and R5 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0023] In some embodiments, A2, A4, and A6 are N in the compound of Formula VI.

[0024] In some embodiments, A in the donor-acceptor ligand has Formula VII: [ka] and an acceptor moiety that is a radical of a compound having In the above formula, R6, R7, and R8 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0025] In some embodiments, A2, A4, and A6 in the compound of Formula VII are N.

[0026] In some embodiments, A in the donor-acceptor ligand has Formula VIII: [ka] and an acceptor moiety that is a radical of a compound having In the above formula, A7 to A 10 independently comprises C or N; R9 is hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0027] In some embodiments, A3 is N and R9 is H in the compound of Formula VIII.

[0028] In some embodiments, A1, A3, A6, A8, A9, and A 10 are N in the compound of formula VIII.

[0029] In some embodiments, A in the donor-acceptor ligand has formula IX: [ka] and an acceptor moiety that is a radical of a compound having In the above formula, A 11 ~A 14 independently contains C or N, and A 11 ~A 14 at least one of is N; X1 is O, S, or NR 12 and; R 10 and R 11 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 12 is hydrogen, C 1~10 Alkyl, C 6~18 It is aryl or heteroaryl.

[0030] In some embodiments, in the compound of formula IX, A 12 and A 13 is N and R 10 and R 11 are each independently H or phenyl.

[0031] In some embodiments, A in the donor-acceptor ligand has the formula X: [ka] and an acceptor moiety that is a radical of a compound having In the above formula, A 15 ~A 22 independently comprises C or N; X2 is O or S; R 13 , R 14 , and R 15 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10Haloalkyl, C(O)C 1~3 Haloalkyl, SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0032] In some embodiments, A in the donor-acceptor ligand has formula XI: [ka] and an acceptor moiety that is a radical of a compound having In the above formula, A 23 ~A 34 independently comprises C or N; R 16 , R 17 , and R 18 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0033] In some embodiments, in the compound of formula XI, A 23 and A 26 is N and R 16 , R 17 , and R 18 is H.

[0034] In some embodiments, A in the donor-acceptor ligand has the formula XII: [ka] and an acceptor moiety that is a radical of a compound having In the above formula, A 35 ~A 38independently comprises C or N; X3 is O, S, or NR21; R 19 and R 20 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 21 is hydrogen, C 1~10 Alkyl, C 6~18 It is aryl or heteroaryl.

[0035] In some embodiments, R 19 and R 20 is H in the compound of formula XII.

[0036] In some embodiments, A in the donor-acceptor ligand has Formula XIII: [ka] and an acceptor moiety that is a radical of a compound having In the above formula, A 39 and A 40 independently comprises C or N; X4 to X7 independently include C, O, S, N, or NR23, and at least one of X4 to X7 is NR 23 and; R 22 But hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3Haloalkyl, SO2H, NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 23 is hydrogen, C 1~10 Alkyl, C 6~18 It is aryl or heteroaryl.

[0037]

[0037] In some embodiments, in the compound of Formula XIII, at least two of X4-X7 are N and R22 is H.

[0038]

[0038] In some embodiments, in the compound of Formula XIII, two of X4-X7 are N and two of X4-X7 are O or S.

[0039]

[0039] In some embodiments, in the compound of Formula XIII, two of X4 to X7 are N and two of X4 to X7 are NH.

[0040] In some embodiments, A in the donor-acceptor ligand is represented by formula XIV: [ka] and an acceptor moiety that is a radical of a compound having In the above formula, A 41 ~A 53 independently contains C or N.

[0041] In some embodiments, in the compound of formula XIV, A 41 ~A 53 At least two of them are N.

[0042] In some embodiments, A in the donor-acceptor ligand is represented by formula XV: [ka] and an acceptor moiety that is a radical of a compound having In the above formula, X8 is C(O) or S(O)2; X9 is CR 26 R 27 , C(O), or S(O)2; R 24 and R 25 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 26 and R 27 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0043] In some embodiments, in the compound of formula XV, X8 is C(O) and R 24 and R 25 is H.

[0044]

[0044] In some embodiments, in the compound of Formula XV, X9 is S(O)2, C(O), or C(CH3)2.

[0045] In some embodiments, A in the donor-acceptor ligand is represented by formula XVI: [ka] and an acceptor moiety that is a radical of a compound having In the above formula, A 54 ~A 61 independently comprises C or N; X 10 is CR 30 R 31 , S, O, or S(O)2; R 28 and R 29 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 30 and R 31 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0046] In some embodiments, in the compound of Formula XVI, A 54 and A 61 At least one of them is N.

[0047] In some embodiments, A in the donor-acceptor ligand has the formula XVII: [ka] and an acceptor moiety that is a radical of a compound having In the above formula, R 32 is -SO2-(C 6~18 aryl), -CN, -C(O)-(C 6~18 aryl), -C(O)-(C 6~18 aryl)-C(O)-(C 6~18 aryl), -SO2-(C 6~18 aryl)-SO2-(C 6~18 aryl), or -B-(C 6~18 aryl)2; R 33 and R 34 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, SO2H, NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0048] In some embodiments, D in the donor-acceptor ligand is: (i') Compound of Formula XVIII: [ka] (Wherein, D1 to D8 independently contain C or N; X 11 But O, S, NR 37 , C.R. 38 R 39 , and S.R. 40 R 41 selected from the group consisting of: R 35 and R 36 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 37 , R 38 , R 39 , R 40 , and R 41 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (ii') Compound of formula XIX: [ka] (In the formula, D9~D 16が independently containing C or N; R 42 and R 45 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (iii') Compound of formula XX: [ka] (In the formula, D 17 ~D 24 independently comprises C or N; X 12 But O, S, NR 48 , C.R. 49 R 50 , and S.R. 51 R 52 selected from the group consisting of: R 46 and R 47 are independently hydrogen, C 1~10 Alkyl, C 2~10Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 48 , R 49 , R 50 , R 51 , and R 52 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (iv') Compound of formula XXI: [ka] (In the formula, D 25 ~D 32 independently comprises C or N; X 12 But O, S, NR 55 , C.R. 56 R 57 , and S.R. 58 R 59 selected from the group consisting of: R 53 and R 54 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 55 , R 56 , R 57 , R 58 , and R 59 are independently hydrogen, C 1~10 Alkyl, C 6~18aryl, or heteroaryl; or (v') Compound of Formula XXII: [ka] (In the formula, D 33 ~D 42 independently comprises C or N; R 60 and R 61 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl) is a donor site containing a radical of

[0049] In some embodiments, D in the donor-acceptor ligand is a donor moiety selected from the group consisting of radicals of the following compounds: [ka] [ka] [ka] [ka] [ka]

[0050] In some embodiments, D in the donor-acceptor ligand is represented by Formula XVIII: [ka] is a donor moiety, which is a radical of a compound having In the above formula, D1 to D8 independently contain C or N; X 11 O, S, NR 37 , C.R. 38 R 39 , and S.R. 40 R 41 selected from the group consisting of: R 35 and R 36 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 37 , R 38 , R 39 , R 40 , and R 41 are each independently hydrogen, C 1~10 Alkyl, C 6~18 It is aryl or heteroaryl.

[0051] In some embodiments, in the compound of Formula XVIII, D1-D8 are C and X 11 is C(CH3)2.

[0052] In some embodiments, in the compound of Formula XVIII, R 35 or R 36 At least one of is a carbazole, a diphenylamine, an acridan, or a phenoxamine.

[0053] In some embodiments, D in the donor-acceptor ligand is represented by formula XIX: [ka] is a donor moiety, which is a radical of a compound having In the above formula, D9 to D 16 independently comprises C or N; R 42 ~R 45 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0054] In some embodiments, in the compound of formula XIX, D9 to D 16 is C.

[0055] In some embodiments, in the compound of formula XIX, R 42 ~R 45 At least one of the 1~10 alkyl, carbazole, or diphenylamine.

[0056] In some embodiments, D in the donor-acceptor ligand has the formula XX: [ka] is a donor moiety, which is a radical of a compound having In the above formula, D 17 ~D 24 independently comprises C or N; X 12 But O, S, NR 48 , C.R. 49 R 50 , and S.R. 51 R 52 selected from the group consisting of: R 46 and R47 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 48 , R 49 , R 50 , R 51 , and R 52 are independently hydrogen, C 1~10 Alkyl, C 6~18 It is aryl or heteroaryl.

[0057] In some embodiments, D in the donor-acceptor ligand is of formula XXI: [ka] is a donor moiety, which is a radical of a compound having In the above formula, D 25 ~D 32 independently comprises C or N; X 12 But O, S, NR 55 , C.R. 56 R 57 , and S.R. 58 R 59 selected from the group consisting of: R 53 and R 54 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18is a haloaryl; R 55 , R 56 , R 57 , R 58 , and R 59 are independently hydrogen, C 1~10 Alkyl, C 6~18 It is aryl or heteroaryl.

[0058] In some embodiments, D in the donor-acceptor ligand is represented by Formula XXII: [ka] is a donor moiety, which is a radical of a compound having In the above formula, D 33 ~D 42 independently comprises C or N; R 60 and R 61 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0059] In some embodiments, in the compound of Formula XXII, D 33 ~D 42 is C and R 60 and R 61 is H.

[0060] In some embodiments, the donor-acceptor ligand is selected from the group consisting of radicals of the following compounds: [ka]

[0061] The present disclosure also provides lighting devices comprising the nanostructure compositions.

[0062]

[0062] In some embodiments, the lighting device is a touchscreen, a monitor, a television, a mobile phone, or a light emitting diode.

[0063]

[0063] In some embodiments, the lighting device is a light emitting diode.

[0064] The present disclosure provides a method for displacing a first ligand on a nanostructure with a second ligand, comprising mixing a reaction mixture containing a population of nanostructures having a first ligand bound to the nanostructure and a second ligand, a donor-acceptor ligand, such that the second ligand displaces the first ligand and becomes bound to the nanostructure, the donor-acceptor ligand having a structure represented by Formula I or Formula II: D d -A a -FG f (I) or A a -D d -FG f (II) and In the above formula, FG is -OH, -SH, -NH2, -CO2H, -P(O)(OH)2, -P(O)OH, or -SO3H; D is a donor moiety comprising a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; A is an acceptor moiety that independently for each occurrence comprises a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer of 1 to 4.

[0065] In some embodiments, the population of nanostructures comprises 1 to 5 populations of nanostructures, hi some embodiments, the population of nanostructures comprises 2 populations of nanostructures.

[0066] In some embodiments, the nanostructure comprises a core selected from the group consisting of InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnTe, ZnSeTe, ZnS, ZnSSe, InAs, InGaAs, and InAsP, hi some embodiments, the nanostructure comprises a core of InP.

[0067] In some embodiments, the nanostructure comprises at least one shell.

[0068] In some embodiments, the nanostructure comprises a ZnS shell.

[0069] In some embodiments, A in the donor-acceptor ligand is: (i) A compound of formula V: [ka] (Wherein, A1 to A6 independently contain C or N, and at least one of A1 to A6 is N; R1, R2, and R3 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (ii) A compound of formula IX: [ka] (In the formula, A 11 ~A 14 independently contains C or N, and A 11 ~A 14 at least one of is N; X1 is O, S, or NR 12 and; R 10 and R 11 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 12 is hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (iii) A compound of formula X: [ka] (In the formula, A 15 ~A 22 independently comprises C or N; X2 is O or S; R 13 , R 14 , and R 15 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (iv) A compound of formula XI: [ka] (In the formula, A 23 ~A 34 independently comprises C or N; R 16 , R 17 , and R 18 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (v) A compound of formula XII: [ka] (In the formula, A 35 ~A 38 independently comprises C or N; X3 is O, S, or NR 21 and; R 19 and R 20 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 21 is hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (vi) Compound of formula XIII: [ka] (In the formula, A 39 and A40 independently comprises C or N; X4 to X7 are independently C, O, S, or NR 23 and at least one of X4 to X7 is NR 23 and; R 22 But hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 23 But hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (vii) Compound of formula XIV: [ka] (In the formula, A 41 ~A 53 independently contain C or N); or (viii) Compound of formula XV: [ka] (Wherein X8 is C(O) or S(O)2; X9 is CR 26 R 27 , C(O), or S(O)2; R 24 and R 25 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 26 and R 27 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (ix) Compound of formula XVI: [ka] (In the formula, A 54 ~A 61 independently comprises C or N; X 10 But, CR 30 R 31 , S, O, or S(O)2; R 28 and R 29 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 30 and R 31 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (x) A compound of formula XVII: [ka] (In the formula, R 32 is -SO2-(C 6~18 aryl), -CN, -C(O)-(C 6~18 aryl), -C(O)-(C 6~18 aryl)-C(O)-(C 6~18 aryl), -SO2-(C 6~18 aryl)-SO2-(C 6~18 aryl), or -B-(C 6~18 aryl)2; R 33 is hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 34 is hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl) is an acceptor site containing a radical of

[0070] In some embodiments, D in the donor-acceptor ligand is: (i') Compound of Formula XVIII: [ka] (Wherein, D1 to D8 independently contain C or N; X 11 O, S, NR 37 , C.R. 38 R 39 , and S.R. 40 R 41 selected from the group consisting of: R 35 and R 36 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 37 , R 38 , R 39 , R 40 , and R 41 are each independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (ii') Compound of formula XIX: [ka] (In the formula, D9~D 16 independently comprises C or N; R 42 and R 45 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C6~18 haloaryl); or (iii') Compound of formula XX: [ka] (In the formula, D 17 ~D 24 independently comprises C or N; X 12 But O, S, NR 48 , C.R. 49 R 50 , and S.R. 51 R 52 selected from the group consisting of: R 46 and R 47 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 48 , R 49 , R 50 , R 51 , and R 52 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (iv') Compound of formula XXI: [ka] (In the formula, D 25 ~D 32 independently comprises C or N; X 12 But O, S, NR 55 , C.R. 56 R 57 , and S.R. 58 R 59 selected from the group consisting of: R 53and R 54 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 55 , R 56 , R 57 , R 58 , and R 59 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (v') Compound of Formula XXII: [ka] (In the formula, D 33 ~D 42 independently comprises C or N; R 60 and R 61 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl) is a donor site containing a radical of

[0071] In some embodiments, the secondary ligand replaces about 30 to about 100% of the moles of the primary ligand on the nanostructure.

[0072] In some embodiments, the secondary ligand replaces about 40 to about 100% of the moles of the primary ligand on the nanostructure.

[0073] In some embodiments, the mixture is at a temperature of about 20 to about 100°C.

[0074]

[0074] The present disclosure provides:

[0075] (a) at least one population of nanostructures comprising ligands bound to the nanostructures;

[0076] (b) at least one donor-acceptor ligand comprising at least one terminal functional group, the at least one donor-acceptor ligand being attached to the surface of the nanostructure; Also provided is a nanostructure film layer comprising:

[0075]

[0077] In some embodiments, the nanostructure film layer comprises 1 to 5 populations of nanostructures, hi some embodiments, the nanostructure film layer comprises 2 populations of nanostructures.

[0076]

[0078] In some embodiments, at least one population of nanostructures in the nanostructure film layer comprises a core selected from the group consisting of InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnTe, ZnSeTe, ZnS, ZnSSe, InAs, InGaAs, and InAsP, hi some embodiments, a population of nanostructures in the nanostructure film layer comprises a core of InP.

[0077]

[0079] In some embodiments, at least one population of nanostructures in the nanostructure film layer comprises a weight percentage of from about 0.0001% to about 5% of the total weight of the nanostructure film layer.

[0078]

[0080] In some embodiments, the donor-acceptor ligand in the nanostructure film layer has Formula I or Formula II: D d -A a -FG f (I) or A a -D d -FG f (II) wherein FG is -OH, -SH, -NH, -COH, -P(O)(OH), -P(O)OH, or -SOH; D is a donor moiety comprising a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; A is an acceptor moiety that independently for each occurrence comprises a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer from 1 to 4. It has.

[0079]

[0081] In some embodiments, A in the donor-acceptor ligand is (i) A compound of formula V: [ka] (Wherein, A1 to A6 independently contain C or N, and at least one of A1 to A6 is N; R1, R2, and R3 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (ii) A compound of formula IX: [ka] (In the formula, A 11 ~A 14 independently contains C or N, and A 11 ~A 14 at least one of is N; X1 is O, S, or NR 12 and; R 10 and R 11 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 12 But hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (iii) A compound of formula X: [ka] (In the formula, A 15 ~A 22 independently comprises C or N; X2 is O or S; R 13 , R 14 , and R 15 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18haloaryl); or (iv) A compound of formula XI: [ka] (In the formula, A 23 ~A 34 independently comprises C or N; R 16 , R 17 , and R 18 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (v) A compound of formula XII: [ka] (In the formula, A 35 ~A 38 independently comprises C or N; X3 is O, S, or NR 21 and; R 19 and R 20 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 21 is hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (vi) Compound of formula XIII: [ka] (In the formula, A 39 and A 40 independently comprises C or N; X4 to X7 are independently C, O, S, or NR 23 and at least one of X4 to X7 is NR 23 and; R 22 is hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 23 But hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (vii) Compound of formula XIV: [ka] (In the formula, A 41 ~A 53 independently contain C or N); or (viii) Compound of formula XV: [ka] wherein X8 is C(O) or S(O)2; X9 is CR 26 R 27 , C(O), or S(O)2; R 24 and R 25 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 26 and R 27 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (ix) Compound of formula XVI: [ka] (In the formula, A 54 ~A 61 independently comprises C or N; X 10 is CR 30 R 31 , S, O, or S(O)2; R 28 and R 29 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 30 and R 31 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (x) A compound of formula XVII: [ka] (In the formula, R 32 But -SO2-(C 6~18 aryl), -CN, -C(O)-(C 6~18 aryl), -C(O)-(C 6~18 aryl)-C(O)-(C 6~18 aryl), -SO2-(C 6~18 aryl)-SO2-(C 6~18 aryl), or -B-(C 6~18 aryl)2; R 33 But hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 34 But hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl) is an acceptor site containing a radical of

[0080]

[0082] In some embodiments, D in the donor-acceptor ligand is (i') Compound of Formula XVIII: [ka] (Wherein, D1 to D8 independently contain C or N; X 11 But O, S, NR 37 , C.R. 38 R 39 , and S.R. 40 R 41 selected from the group consisting of: R 35 and R 36 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 37 , R 38 , R 39 , R 40 , and R 41 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (ii') Compound of formula XIX: [ka] (In the formula, D9~D 16 independently comprises C or N; R 42 and R 45 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (iii') Compound of formula XX: [ka] (In the formula, D 17 ~D 24 independently comprises C or N; X 12 But O, S, NR 48 , C.R. 49 R 50 , and S.R. 51 R 52 selected from the group consisting of: R 46 and R 47 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 48 , R 49 , R 50 , R 51 , and R 52 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (iv') Compound of formula XXI: [ka] (In the formula, D 25 ~D 32 independently comprises C or N; X 12 But O, S, NR 55 , C.R. 56 R 57 , and S.R.58 R 59 selected from the group consisting of: R 53 and R 54 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 55 , R 56 , R 57 , R 58 , and R 59 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (v') Compound of Formula XXII: [ka] (In the formula, D 33 ~D 42 independently comprises C or N; R 60 and R 61 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl) is a donor site containing a radical of

[0081]

[0083] In some embodiments, at least one population of nanostructures in the nanostructure film layer comprises at least one shell.

[0082]

[0084] In some embodiments, at least one population of nanostructures in the nanostructure film layer comprises two shells.

[0083]

[0085] In some embodiments, a nanostructure in the population of nanostructures is a quantum dot.

[0084]

[0086] In some embodiments, the quantum dots are InP and / or ZnSe quantum dots.

[0085]

[0087] The present disclosure provides: (a) a first conductive layer; (b) a second conductive layer; (c) a light emitting diode including a light emitting layer between a first conductive layer and a second conductive layer, Also provided is a light-emitting diode in which the light-emitting layer comprises at least one population of nanostructures comprising donor-acceptor ligands, the donor-acceptor ligands comprising at least one terminal functional group, the at least one terminal functional group being attached to the surface of the nanostructures.

[0086]

[0088] In some embodiments, the light-emitting layer comprises 1 to 5 populations of nanostructures, hi some embodiments, the light-emitting layer comprises 2 populations of nanostructures.

[0087]

[0089] In some embodiments, at least one population of nanostructures in the light-emitting layer comprises a core selected from the group consisting of InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnTe, ZnSeTe, ZnS, ZnSSe, InAs, InGaAs, and InAsP, hi some embodiments, the nanostructures comprise a core of InP.

[0088]

[0090] In some embodiments, at least one population of nanostructures in the light-emitting layer comprises a weight percentage of from about 0.0001 to about 5% based on the total weight of the nanostructure film layer.

[0089]

[0091] In some embodiments, the donor-acceptor ligands of the population of nanostructures have Formula I or Formula II: D d -A a -FG f (I) or A a -D d -FG f (II) wherein FG is -OH, -SH, -NH, -COH, -P(O)(OH), -P(O)OH, or -SOH; D is a donor moiety comprising a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; A is an acceptor moiety that independently for each occurrence comprises a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer from 1 to 4. It has.

[0090]

[0092] In some embodiments, A in the donor-acceptor ligand is (i) A compound of formula V: [ka] (Wherein, A1 to A6 independently contain C or N, and at least one of A1 to A6 is N; R1, R2, and R3 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (ii) A compound of formula IX: [ka] (In the formula, A 11 ~A 14 independently contains C or N, and A 11 ~A 14 at least one of is N; X1 is O, S, or NR 12 and; R 10 and R 11 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 12 But hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (iii) A compound of formula X: [ka] (In the formula, A 15 ~A 22 independently comprises C or N; X2 is O or S; R 13 , R 14 , and R 15 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (iv) A compound of formula XI: [ka] (In the formula, A 23 ~A 34 independently comprises C or N; R 16 , R 17 , and R 18 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (v) A compound of formula XII: [ka] (In the formula, A 35 ~A 38 independently comprises C or N; X3 is O, S, or NR 21 and; R 19 and R 20 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R21 is hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (vi) Compound of formula XIII: [ka] (In the formula, A 39 and A 40 independently comprises C or N; X4 to X7 are independently C, O, S, or NR 23 and at least one of X4 to X7 is NR 23 and; R 22 is hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 23 But hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (vii) Compound of formula XIV: [ka] (In the formula, A 41 ~A 53 independently contain C or N); or (viii) Compound of formula XV: [ka] wherein X8 is C(O) or S(O)2; X9 is CR 26 R 27 , C(O), or S(O)2; R 24 and R 25are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 26 and R 27 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (ix) Compound of formula XVI: [ka] (In the formula, A 54 ~A 61 independently comprises C or N; X 10 is CR 30 R 31 , S, O, or S(O)2; R 28 and R 29 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 30 and R31 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (x) A compound of formula XVII: [ka] (In the formula, R 32 But -SO2-(C 6~18 aryl), -CN, -C(O)-(C 6~18 aryl), -C(O)-(C 6~18 aryl)-C(O)-(C 6~18 aryl), -SO2-(C 6~18 aryl)-SO2-(C 6~18 aryl), or -B-(C 6~18 aryl)2; R 33 But hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 34 But hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C6~18 haloaryl) is an acceptor site containing a radical of

[0091]

[0093] In some embodiments, D in the donor-acceptor ligand is (i') Compound of Formula XVIII: [ka] (Wherein, D1 to D8 independently contain C or N; X 11 But O, S, NR 37 , C.R. 38 R 39 , and S.R. 40 R 41 selected from the group consisting of: R 35 and R 36 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 37 , R 38 , R 39 , R 40 , and R 41 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (ii') Compound of formula XIX: [ka] (In the formula, D9~D 16 independently comprises C or N; R 42 and R 45 are independently hydrogen, C 1~10 Alkyl, C2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (iii') Compound of formula XX: [ka] (In the formula, D 17 ~D 24 independently comprises C or N; X 12 But O, S, NR 48 , C.R. 49 R 50 , and S.R. 51 R 52 selected from the group consisting of: R 46 and R 47 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 48 , R 49 , R 50 , R 51 , and R 52 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (iv') Compound of formula XXI: [ka] (In the formula, D 25 ~D 32independently comprises C or N; X 12 But O, S, NR 55 , C.R. 56 R 57 , and S.R. 58 R 59 selected from the group consisting of: R 53 and R 54 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 55 , R 56 , R 57 , R 58 , and R 59 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (v') Compound of Formula XXII: [ka] (In the formula, D 33 ~D 42 independently comprises C or N; R 60 and R 61 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl) is a donor site containing a radical of

[0092]

[0094] In some embodiments, the first conductive layer of the light emitting diode comprises indium tin oxide, indium zinc oxide, tin dioxide, zinc oxide, magnesium, aluminum, aluminum-lithium, calcium, magnesium-indium, magnesium-silver, silver, gold, or a mixture thereof.

[0093]

[0095] In some embodiments, the first conductive layer of the light emitting diode comprises indium tin oxide.

[0094]

[0096] In some embodiments, the second conductive layer of the light emitting diode comprises indium tin oxide, indium zinc oxide, titanium dioxide, tin oxide, zinc sulfide, silver, or a mixture thereof.

[0095]

[0097] In some embodiments, the second conductive layer of the light emitting diode comprises aluminum.

[0096]

[0098] In some embodiments, the second conductive layer of the light emitting diode comprises gold.

[0097]

[0099] In some embodiments, the light emitting diode further comprises a semiconducting polymer layer.

[0098]

[0100] In some embodiments, the semiconducting polymer layer of the light-emitting diode comprises copper phthalocyanine, 4,4',4''-tris[(3-methylphenyl)phenylamino]triphenylamine (m-MTDATA), 4,4',4''-tris(diphenylamino)triphenylamine (TDATA), 4,4',4''-tris[2-naphthyl(phenyl)amino]triphenylamine (2T-NATA), polyaniline / dodecylbenzenesulfonic acid, poly(3,4-ethylenedioxythiophene) / polystyrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid, or polyaniline / poly(4-styrenesulfonate).

[0099]

[0101] In some embodiments, the semiconducting polymer layer of the light emitting diode comprises PEDOT / PSS.

[0100]

[0102] In some embodiments, the light emitting diode further comprises a first transport layer.

[0101]

[0103] In some embodiments, the first transport layer of the light emitting diode comprises N,N'-di(naphthalen-1-yl)-N,N'-bis(4-vinylphenyl)-4,4'-diamine, poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl))diphenylamine)], or poly(9-vinylcarbazole).

[0102]

[0104] In some embodiments, the first transport layer of the light emitting diode comprises N,N'-di(naphthalen-1-yl)-N,N'-bis(4-vinylphenyl)-4,4'-diamine.

[0103]

[0105] In some embodiments, the light emitting diode further comprises a second transport layer.

[0104]

[0106] In some embodiments, the second transport layer of the light emitting diode is selected from the group consisting of 1,3-bis(3,5-dipyrid-3-ylphenyl)benzene (B3PyPB), bathocuproine, bathophenanthroline, 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole, 2-(4-biphenylyl)-5-phenyl-1,3,4-oxadiazole, 3,5-bis(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole, bis(8-hydroxy-2-methylquinoline)-(4- Examples of suitable bis(m-phenylphenoxy)aluminum include 2,5-bis(1-naphthyl)-1,3,4-oxadiazole, 3,5-diphenyl-4-(1-naphthyl)-1H-1,2,4-triazole, 1,3,5-tri(m-pyridin-3-ylphenyl)benzene (TmPyPB), 2,2',2''-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi), tris-(8-hydroxyquinoline)aluminum, TiO2, ZnO, SnO2, SiO2, ZrO2, and ZnMgO.

[0105]

[0107] In some embodiments, the second transport layer of the light emitting diode comprises ZnMgO.

[0106]

[0108] In some embodiments, the first transport layer of the light-emitting diode comprises indium tin oxide, the second conductive layer comprises aluminum, the semiconducting polymer layer comprises PEDOT / PSS, the first transport layer comprises N,N'-di(naphthalen-1-yl)-N,N'-bis(4-vinylphenyl)-4,4'-diamine, and the second transport layer comprises ZnMgO.

[0107]

[0109] In some embodiments, the first transport layer of the light-emitting diode comprises indium tin oxide, the second conductive layer comprises gold, the semiconducting polymer layer comprises PEDOT / PSS, and the first transport layer comprises N,N'-di(naphthalen-1-yl)-N,N'-bis(4-vinylphenyl)-4,4'-diamine.

[0108] BRIEF DESCRIPTION OF THE DRAWINGS

[0110] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate the present invention and, together with the description, serve to further explain the principles of the invention and to enable one skilled in the art to make and use the invention. [Brief explanation of the drawings]

[0109] [Figure 1]

[0111] FIG. 1 is a schematic diagram illustrating a device comprising a quantum dot emissive layer with coordinated thermally activated delayed fluorescence (TADF) or bipolar ligands between a cathode and an anode layer. [Figure 2]

[0112] Schematic diagram showing the emission mechanism of quantum dots containing TADF or bipolar ligands. As shown in Figure 2, the singlet energies of the host material, bipolar ligand, and TADF ligand (S14, S13, and S12, respectively) are higher than the singlet energy of quantum dots (QDs) due to energy transfer from the organic materials to the quantum dots via Förster resonance energy transfer (FRET) and Dexter energy transfer (DET). DETAILED DESCRIPTION OF THE INVENTION

[0110] Detailed Description of the Invention

[0113] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The definitions provided below supplement those in the art and are directed to this application and are not to be attributed to any related or unrelated case, e.g., any commonly owned patent or application. Although any methods and materials similar or equivalent to those described herein can be used to perform the tests, preferred materials and methods are described herein. Therefore, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0111]

[0114] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a nanostructure" includes a plurality of such nanostructures, and so forth.

[0112]

[0115] As used herein, the term "about" indicates that the numerical value of a given quantity varies by ±10%. For example, "about 100 nm" encompasses a range of sizes from 90 nm to 110 nm, inclusive.

[0113]

[0116] A "nanostructure" is a structure having at least one region or characteristic dimension having a dimension less than about 500 nm. In some embodiments, a nanostructure has a dimension less than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, or less than about 10 nm. Typically, the region or characteristic dimension is along the shortest axis of the structure. Examples of such structures include nanowires, nanorods, nanotubes, branched nanostructures, nanotetrapods, tripods, bipods, nanocrystals, nanodots, quantum dots, nanoparticles, and the like. Nanostructures can be, for example, substantially crystalline, substantially monocrystalline, polycrystalline, amorphous, or a combination thereof. In some embodiments, each of the three dimensions of the nanostructure is less than about 500 nm, less than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, or less than about 10 nm.

[0114]

[0117] The term "heterostructure," as used in reference to nanostructures, refers to a nanostructure characterized by at least two different and / or distinguishable types of material. Typically, one region of the nanostructure contains a first type of material, while a second region of the nanostructure contains a second type of material. In certain embodiments, the nanostructure comprises a core of a first material and at least one shell of a second (or third, etc.) material, with the different types of materials distributed radially, e.g., along the long axis of a nanowire, along the long axes of the arms of a branched nanowire, or along the center of a nanocrystal. The shell may, but need not, completely cover the adjacent material to be considered a shell or for the nanostructure to be considered a heterostructure; for example, a nanocrystal characterized by a core of one material surrounded by small islands of a second material is a heterostructure. In other embodiments, the different types of materials are distributed at different locations within the nanostructure, e.g., along the major (long) axis of a nanowire or along the long axes of the arms of a branched nanowire. Different regions within a heterostructure may comprise entirely different materials, or the different regions may comprise a base material (e.g., silicon) that contains different dopants or the same dopant at different concentrations.

[0115]

[0118] As used herein, the "diameter" of a nanostructure refers to the diameter of a cross section perpendicular to the first axis of the nanostructure, the first axis being the largest difference in length from the second and third axes (the second and third axes being most nearly equal in length). The first axis is not necessarily the longest axis of the nanostructure; for example, in the case of a disk-shaped nanostructure, the cross section would be a substantially circular cross section perpendicular to the short longitudinal axis of the disk. If the cross section is not circular, the diameter is the average of the long and short axes of the cross section. For elongated or high aspect ratio nanostructures, such as nanowires, the diameter is measured in a cross section perpendicular to the longest axis of the nanowire. For spherical nanostructures, the diameter is measured from one side to the other, passing through the center of the sphere.

[0116]

[0119] The terms "crystalline" or "substantially crystalline," when used in connection with nanostructures, generally refer to the nanostructure exhibiting long-range order across one or more dimensions of the structure. Because single-crystal order cannot exist beyond the boundaries of the crystal, those skilled in the art will understand that the term "long-range order" will depend on the absolute size of a particular nanostructure. In this case, "long-range order" will refer to substantial order across at least most of the nanostructure's dimensions. In some instances, the nanostructure may have an oxide or other coating, or may be composed of a core and at least one shell. In such instances, it will be understood that the oxide, shell, or other coating may, but need not, exhibit such order (e.g., may be amorphous, polycrystalline, or otherwise). In such instances, the phrases "crystalline," "substantially crystalline," "substantially monocrystalline," or "monocrystalline" refer to the central core of the nanostructure (excluding any coating layers or shells). As used herein, "crystalline" or "substantially crystalline" is intended to encompass structures containing various defects, stacking disorders, atomic substitutions, and the like, so long as the structure exhibits substantial long-range order (e.g., order over at least about 80% of the length of at least one axis of the nanostructure or its core). Furthermore, it will be understood that the interface between the core and the outer surface of the nanostructure, or the interface between the core and an adjacent shell, or the interface between a shell and an adjacent second shell, may include a non-crystalline region or may even be amorphous. This does not prevent the nanostructure from having crystallinity or substantially crystallinity as defined herein.

[0117]

[0120] The term "monocrystalline" when used with respect to a nanostructure indicates that the nanostructure is substantially crystalline and comprises substantially a single crystal. When used with respect to a nanostructure heterostructure comprising a core and one or more shells, "monocrystalline" indicates that the core is substantially crystalline and comprises substantially a single crystal.

[0118]

[0121] A "nanocrystal" is a nanostructure that is substantially monocrystalline. Thus, a nanocrystal has at least one region or characteristic dimension that is less than about 500 nm. In some embodiments, the dimensions of a nanocrystal are less than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, or less than about 10 nm. The term "nanocrystal" is intended to encompass substantially monocrystalline nanostructures that contain defects, stacking faults, atomic substitutions, and the like, as well as nanostructures that are substantially monocrystalline and free of such defects, faults, or substitutions. In the case of nanocrystal heterostructures comprising a core and one or more shells, the core of the nanocrystal is typically substantially monocrystalline, but the shells need not be. In some embodiments, the three dimensions of the nanocrystal are each less than about 500 nm, less than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, or less than about 10 nm.

[0119]

[0122] The term "quantum dot" (or "dot") refers to a nanocrystal that exhibits quantum or exciton confinement. Quantum dots can be substantially homogeneous in material properties, or in certain embodiments, can be heterogeneous, e.g., comprise a core and at least one shell. The optical properties of quantum dots can be affected by their particle size, chemical composition, and / or surface composition, and can be measured using suitable optical tests available in the art. Tailoring the size of nanocrystals, e.g., in the range of about 1 nm to about 15 nm, allows for photoemission across the entire optical spectrum, enabling diverse color rendering.

[0120]

[0123] A "ligand" is a molecule that can interact (weakly or strongly) with one or more facets of a nanostructure, for example, through covalent, ionic, van der Waals, or other molecular interactions with the surface of the nanostructure.

[0121]

[0124] "Photoluminescence quantum yield" is the ratio of photons emitted to photons absorbed by, for example, a nanostructure or population of nanostructures. As known in the art, quantum yield is typically determined by comparative methods using well-characterized reference samples with known quantum yield values.

[0122]

[0125] As used herein, the term "shell" refers to a material deposited on a core or on a previously deposited shell of the same or different composition, resulting from a single act of depositing the shell material. The exact thickness of the shell depends on the material as well as the precursor input and conversion rate, and can be reported in nanometers or monolayers. As used herein, "target shell thickness" refers to the intended shell thickness used to calculate the amount of precursor required. As used herein, "actual shell thickness" refers to the amount of shell material actually deposited after synthesis, which can be measured by methods known in the art. For example, the actual shell thickness can be measured by comparing the particle diameter determined from transmission electron microscopy (TEM) images of nanocrystals before and after shell synthesis.

[0123]

[0126] As used herein, the term "stable" means a mixture or composition that resists change or decomposition due to internal reaction or due to the action of air, heat, light, electric field, electric current, pressure, or other natural conditions.

[0124]

[0127] The term "full width at half maximum" (FWHM) as used herein is a measure of the size distribution of quantum dots. The emission spectrum of quantum dots generally has a Gaussian curve shape. The width of the Gaussian curve is defined as the FWHM and provides insight into the size distribution. A smaller FWHM corresponds to a narrower size distribution of quantum dot nanocrystals. The FWHM also depends on the maximum emission wavelength.

[0125]

[0128] As used herein, the term "moiety" refers to the radical of a molecule that is linked to another moiety.

[0126]

[0129] As used herein, the term "donor moiety" refers to a molecular fragment that, upon excitation, can donate an electron from its highest occupied molecular orbital to an acceptor moiety. In some embodiments, the donor moiety comprises an amine group, an alkoxy group, or a combination thereof. In some embodiments, the donor moiety is selected from the group consisting of carbazole, benzofurocarbazole, thienocarbazole, indolocarbazole, bicarbazole, amine, diamine, acridan, phenoxazine, phenothiazine, or phenazine.

[0127]

[0130] As used herein, the term "acceptor moiety" refers to a molecular fragment that, when subjected to excitation, can accept an electron from a donor moiety into its lowest unoccupied molecular orbital. In some embodiments, the acceptor moiety comprises a nitro group, a cyano group, a sulfonyl group, a ketone group, or a combination thereof. In some embodiments, the acceptor moiety is selected from the group consisting of diphenyl sulfone, aromatic ketone, triazine, benzonitrile, benzoxazole, quinoxaline, anthroquinone, and heptazine.

[0128]

[0131] As used herein, the term "alkyl" refers to a straight or branched chain, saturated, aliphatic group having the specified number of carbon atoms. In some embodiments, alkyl is a C 1~2 Alkyl, C 1~3 Alkyl, C 1~4 Alkyl, C 1~5 Alkyl, C 1~6 Alkyl, C 1~7 Alkyl, C 1~8 Alkyl, C 1~9 Alkyl, C 1~10 Alkyl, C 1~12 Alkyl, C 1~14 Alkyl, C 1~16 Alkyl, C1~18 Alkyl, C 1~20 Alkyl, C 8~20 Alkyl, C 12~20 Alkyl, C 14~20 Alkyl, C 16~20 Alkyl, or C 18~20 It is an alkyl group. For example, C 1~6 Alkyl includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl. In some embodiments, alkyl is octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or icosanyl.

[0129]

[0132] The term "alkylene," as used herein alone or in combination, refers to a saturated aliphatic group derived from a straight- or branched-chain saturated hydrocarbon linked at two or more positions, such as methylene (-CH-). Unless otherwise specified, the term "alkyl" encompasses "alkylene" groups.

[0130]

[0133] As used herein, the term "alkenyl" refers to a monovalent group derived from a straight- or branched-chain hydrocarbon moiety having at least one carbon-carbon double bond by the removal of a single hydrogen atom. In some embodiments, an alkenyl group containing 2 to 20 carbon atoms is C 2~20 In some embodiments, an alkenyl group containing 2 to 15 carbon atoms is C 2~15 In some embodiments, an alkenyl group containing 2 to 10 carbon atoms is C 2~10 In some embodiments, an alkenyl group containing 2 to 8 carbon atoms is C 2~8 In some embodiments, an alkenyl group containing 2 to 5 carbon atoms is C 2~5Alkenyl. Alkenyl groups include, for example, ethenyl, propenyl, butenyl, and 1-methyl-2-buten-1-yl.

[0131]

[0134] As used herein, "alkynyl" refers to a monovalent group derived from a straight- or branched-chain hydrocarbon moiety having at least one carbon-carbon triple bond by the removal of a single hydrogen atom. In some embodiments, an alkynyl group containing 2 to 20 carbon atoms is C 2~20 In some embodiments, an alkynyl group containing 2 to 15 carbon atoms is C 2~15 Alkynyl. Alkynyl groups containing 2 to 10 carbon atoms are C 2~10 In some embodiments, an alkynyl group containing 2 to 8 carbon atoms is C 2~8 In some embodiments, an alkynyl group containing 2 to 5 carbon atoms is C 2~5 Alkynyl. Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), and 1-propynyl.

[0132]

[0135] As used herein, "alkoxy" refers to an "alkyl-O-" group, where alkyl is defined above. Alkoxy groups include, for example, methoxy or ethoxy.

[0133]

[0136] As used herein, "alkylamino" refers to an R K are each independently hydrogen or an optionally substituted alkyl group as defined herein, and the nitrogen moiety is directly attached to the parent molecule, the formula (—NR K 2) means "substituted amino".

[0134]

[0137] As used herein, "heteroalkyl" refers to an alkyl moiety that is optionally substituted with one or more functional groups, e.g., contains one or more oxygen, sulfur, nitrogen, phosphorus, or silicon atoms in place of a carbon atom.

[0135]

[0138] As used herein, "cycloalkyl" refers to a monovalent or divalent group of 3 to 8, preferably 3 to 5, carbon atoms derived from a saturated cyclic hydrocarbon. A cycloalkyl group can be a monocyclic or polycyclic group. A cycloalkyl is a C 1~3 It can be substituted with alkyl groups or halogens.

[0136]

[0139] As used herein, "carboxy" refers to -COOH, -COOR A , OC(O)H, -OC(O)R A groups containing a carbon-oxygen double bond, such as R A is alkyl, alkenyl, alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, each of which may be optionally substituted. In some embodiments, carboxy is a carboxylic acid, dicarboxylic acid, polycarboxylic acid, or carboxylate.

[0137]

[0140] As used herein, "haloalkyl" refers to at least one halogen attached to the parent molecular group through an alkyl moiety. Suitable haloalkyls for use in the compounds are chloromethyl, 2-fluoroethyl, trifluoromethyl, pentafluoroethyl, and 2-chloro-3-fluorophenyl.

[0138]

[0141] As used herein, "amido" refers to both "aminocarbonyl" and "carbonylamino." When used alone or in combination with other groups, these terms include N(R L R M )-C(O)- or R M C(O)-N(RL )-, and when used internally, -C(O)-N(R L )- or -N(R M )-C(O)-, and R L and R M are each independently hydrogen, alkyl, alicyclic, (alicyclic)aliphatic, aryl, araliphatic, heterocycloaliphatic, (heterocycloaliphatic)aliphatic, heteroaryl, carboxy, sulfanyl, sulfinyl, sulfonyl, (aliphatic)carbonyl, (alicyclic)carbonyl, ((alicyclic)aliphatic)carbonyl, arylcarbonyl, (araliphatic)carbonyl, (heterocycloaliphatic)carbonyl, ((heterocycloaliphatic)aliphatic)carbonyl, (heteroaryl)carbonyl, or (heteroaliphatic)carbonyl, each of which is defined herein and optionally substituted. Exemplary amino groups include alkylamino, dialkylamino, or arylamino. Examples of amido groups include alkylamido (such as alkylcarbonylamino or alkylcarbonylamino), (heterocycloaliphatic)amido, (heteroaralkyl)amido, (heteroaryl)amido, (heterocycloalkyl)alkylamido, arylamido, aralkylamido, (cycloalkyl)alkylamido, or cycloalkylamido.

[0139]

[0142] As used herein, "carboxyalkyl" refers to a carboxylic acid group (-COOH) attached to a lower alkyl group.

[0140]

[0143] As used herein, "heterocycloalkyl" refers to a cycloalkyl substituent having 1 to 5, more typically 1 to 4, heteroatoms in the ring structure. Heteroatoms suitable for use in the compounds are nitrogen, oxygen, and sulfur. Representative heterocycloalkyl moieties include, for example, morpholino, piperazinyl, piperidinyl, and the like.

[0141]

[0144] As used herein, "aryl" or "aromatic" refers to an unsubstituted monocyclic or bicyclic aromatic ring structure having 6 to 14 carbon atoms, i.e., C 6~14 "aryl" refers to an aryl group. Non-limiting exemplary aryl groups include phenyl, naphthyl, phenanthryl, anthracyl, indenyl, azulenyl, biphenyl, biphenylenyl, fluorenyl, terphenyl, pyrenyl, 9,9-dimethyl-2-fluorenyl, anthryl, triphenylenyl, chrysenyl, fluorenylidenephenyl, and 5H-dibenzo[a,d]cycloheptenylidenephenyl. In one embodiment, the aryl group is phenyl, naphthyl, or 9,9-dimethyl-2-fluorenyl.

[0142]

[0145] As used herein, the term "heteroaryl" or "heteroaromatic" refers to unsubstituted monocyclic and bicyclic aromatic ring systems having 5 to 14 ring atoms, i.e., 5- to 14-membered heteroaryl, wherein at least one carbon atom in one of the rings is replaced with a heteroatom independently selected from the group consisting of oxygen, nitrogen, and sulfur. In one embodiment, the heteroaryl contains 1, 2, 3, or 4 heteroatoms independently selected from the group consisting of oxygen, nitrogen, and sulfur. In one embodiment, the heteroaryl has 3 heteroatoms. In another embodiment, the heteroaryl has 2 heteroatoms. In another embodiment, the heteroaryl has 1 heteroatom. In another embodiment, the heteroaryl is a 5- to 10-membered heteroaryl. In another embodiment, the heteroaryl is a 5- or 6-membered heteroaryl. In another embodiment, the heteroaryl is thienyl, which is a 5-membered heteroaryl having 5 ring atoms, e.g., 4 carbon atoms and 1 sulfur atom. In another embodiment, the heteroaryl is pyridyl, which is a 6-membered heteroaryl having 6 ring atoms, e.g., 5 carbon atoms and 1 nitrogen atom. Non-limiting examples of heteroaryl groups include thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furyl, benzofuryl, pyranyl, isobenzofuranyl, benzoxazonyl, chromenyl, xanthenyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, isoindolyl, 3H-indolyl, indolyl, indazolyl, purinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, cinnolinyl, quinazolinyl, pteridinyl, 4aH-carbazolyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, thiazolyl, isothiazolyl, phenothiazolyl, isoxazolyl, furazanyl, and phenoxazinyl.In one embodiment, heteroaryl is thienyl (e.g., thien-2-yl and thien-3-yl), furyl (e.g., 2-furyl and 3-furyl), pyrrolyl (e.g., 1H-pyrrol-2-yl and 1H-pyrrol-3-yl), imidazolyl (e.g., 2H-imidazol-2-yl and 2H-imidazol-4-yl), pyrazolyl (e.g., 1H-pyrazol-3-yl, 1H-pyrazol-4-yl and 1H-pyrazol-5-yl), pyridyl (e.g., pyridin-2-yl, pyridin-3-yl and pyridin-4-yl), pyrimidinyl (e.g., pyrimidin-2-yl, pyridin-3-yl and pyridin-4-yl), pyrimidine (e.g., pyrimidine-2-yl, pyrimidine-3-yl and pyrimidine-4-yl), pyrimidine-5-yl, pyrimidine-6-yl, pyrimidine-7-yl, pyrimidine-8-yl, pyrimidine-9-yl, pyrimidine-10-yl, pyrimidine-11-yl, pyrimidine-12-yl, pyrimidine-13-yl, pyrimidine-14-yl), pyrimidine-15-yl, pyrimidine-16-yl, pyrimidine-17-yl, pyrimidine-18-yl, pyrimidine-19-yl, pyrimidine-20-yl, pyrimidine-21-yl, pyrimidine-22-yl, pyrimidine-23-yl, pyrimidine-24-yl, pyrimidine-25-yl, pyrimidine-26-yl, pyrimidine-27-yl, pyrimidine-28-yl, pyrimidine-29-yl, pyrimidine-29-yl, pyrimidine-29- -yl, pyrimidin-4-yl and pyrimidin-5-yl), thiazolyl (e.g., thiazol-2-yl, thiazol-4-yl and thiazol-5-yl), isothiazolyl (e.g., isothiazol-3-yl, isothiazol-4-yl and isothiazol-5-yl), oxazolyl (e.g., oxazol-2-yl, oxazol-4-yl and oxazol-5-yl), isoxazolyl (e.g., isoxazol-3-yl, isoxazol-4-yl and isoxazol-5-yl), or indazolyl (e.g., 1H-indazol-3-yl). The term "heteroaryl" also includes possible N-oxides. A non-limiting exemplary N-oxide is pyridyl N-oxide.

[0143]

[0146] As used herein, the term "radical" as known to those skilled in the chemical arts means a chemical species that has an unpaired valence electron.

[0144]

[0147] Unless otherwise specified, the ranges set forth herein are inclusive.

[0145]

[0148] A variety of additional terms are defined or characterized herein.

[0146] Nanostructure composition

[0149] In some embodiments, the present disclosure provides (a) at least one population of nanostructures; and (b) at least one donor-acceptor ligand; wherein the donor-acceptor ligand comprises at least one terminal functional group, and the at least one terminal functional group is attached to a surface of the nanostructure.

[0147]

[0150] In some embodiments, the nanostructures are quantum dots.

[0148]

[0151] In some embodiments, the donor-acceptor ligand is a thermally activated delayed fluorescence (TADF) ligand.

[0149]

[0152] In some embodiments, the donor-acceptor ligand comprises at least one donor moiety attached to at least one terminal functional group. In some embodiments, the donor-acceptor ligand comprises at least one acceptor moiety attached to at least one terminal functional group.

[0150]

[0153] In some embodiments, the present disclosure provides (a) at least one population of nanostructures; and (b) at least one donor-acceptor ligand attached to the surface of the nanostructure; The donor-acceptor ligands are: (i) a donor-acceptor ligand of formula (I) D d -A a -FG f (I) wherein FG is -OH, -SH, -NH, -COH, -P(O)(OH), -P(O)OH, or -SOH; D is a donor moiety comprising a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; A is an acceptor moiety that independently for each occurrence comprises a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer from 1 to 4; or (ii) a donor-acceptor ligand of formula (II) A a -D d -FG f (II) wherein FG is -OH, -SH, -NH, -COH, -P(O)(OH), -P(O)OH, or -SOH; A is an acceptor moiety comprising a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; D is a donor moiety that comprises, independently for each occurrence, a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer from 1 to 4); and (iii) any combination thereof; The present invention provides a nanostructure composition comprising:

[0151]

[0154] In some embodiments, the nanostructures are quantum dots.

[0152]

[0155] In some embodiments, the present disclosure provides (a) at least one population of nanostructures, the nanostructures comprising ligands bound to the nanostructures; and (b) at least one donor-acceptor ligand bound to the surface of the nanostructure; A nanostructure composition comprising: The donor-acceptor ligand is (i) a donor-acceptor ligand of formula (III) [ka] wherein D is a donor moiety that comprises, independently for each occurrence, a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; A is an acceptor moiety comprising a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer from 1 to 4; or (ii) a donor-acceptor ligand of formula (IV) [ka] wherein A is an acceptor moiety comprising a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; D is a donor moiety that comprises, independently for each occurrence, a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer from 1 to 4; or (iii) any combination thereof; The present invention provides a nanostructure composition comprising:

[0153]

[0156] In some embodiments, the nanostructure composition further comprises an organic resin.

[0154]

[0157] In some embodiments, the nanostructures are quantum dots.

[0155] Nanostructured film layer

[0158] In some embodiments, the present invention provides a method for treating a cancer cell comprising: (a) at least one population of nanostructures, the nanostructures comprising ligands bound to the nanostructures; and (b) at least one donor-acceptor ligand bound to the nanostructure; a nanostructure film layer comprising:

[0156]

[0159] In some embodiments, the nanostructure film layer further comprises an organic resin.

[0157]

[0160] In some embodiments, the nanostructures are quantum dots.

[0158] lighting devices

[0161] In some embodiments, the present invention provides a method for treating a cancer cell comprising: (a) first conductive layer; (b) a second conductive layer; and (c) a light-emitting layer between the first conductive layer and the second conductive layer; wherein the light-emitting layer comprises at least one population of nanostructures comprising donor-acceptor ligands bound to the nanostructures.

[0159]

[0162] In some embodiments, the light emitting diode is a quantum dot light emitting diode.

[0160]

[0163] In some embodiments, the donor-acceptor ligand comprises at least one acceptor moiety attached to at least one terminal functional group. In some embodiments, the donor-acceptor ligand comprises at least one donor moiety attached to at least one terminal functional group. In some embodiments, the nanostructure comprises a combination of a donor-acceptor ligand comprising at least one acceptor moiety attached to at least one terminal functional group and a donor-acceptor ligand of at least one donor moiety attached to at least one terminal functional group.

[0161] nanostructures

[0164] Quantum dots (or other nanostructures) for use in the present invention can be made from any suitable material, preferably inorganic, more preferably inorganic conductive or semiconducting materials. Suitable semiconducting materials include any type of semiconductor, including Group II-VI, Group III-V, Group IV-VI, and Group IV semiconductors. Suitable semiconductor materials include, but are not limited to, Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, SiN, GeN, AlO, and combinations thereof.

[0162]

[0165] The synthesis of Group II-VI nanostructures is described in U.S. Patent No. 6,225,198, U.S. Patent No. 6,322,901, U.S. Patent No. 6,207,229, U.S. Patent No. 6,607,829, U.S. Patent No. 6,861,155, U.S. Patent No. 7,060,243, U.S. Patent No. 7,125,605, U.S. Patent No. 7,374,824, U.S. Patent No. 7,566,476, U.S. Patent No. 8,101,234, and U.S. Patent No. 8,158,193, as well as U.S. Patent Application Publication Nos. 2011 / 0262752 and 2011 / 0263062. In some embodiments, the core is a II-VI nanocrystal selected from the group consisting of ZnO, ZnSe, ZnS, ZnTe, CdO, CdSe, CdS, CdTe, HgO, HgSe, HgS, and HgTe. In some embodiments, the core is a nanocrystal selected from the group consisting of ZnSe, ZnS, CdSe, and CdS.

[0163]

[0166] Although II-VI nanostructures, such as CdSe and CdS quantum dots, can exhibit desirable luminescence behavior, the toxicity of cadmium limits the applications in which these nanostructures can be used. Therefore, less toxic alternatives with favorable luminescence properties are highly desirable. In general, III-V nanostructures, and InP-based nanostructures in particular, are the best alternatives among known cadmium-based materials due to their consistent luminescence range.

[0164]

[0167] In some embodiments, the nanostructures are cadmium-free. As used herein, the term "cadmium-free" refers to nanostructures containing less than 100 ppm cadmium by weight. The Restriction of Hazardous Substances (RoHS) compliance definition requires that cadmium in raw homogeneous precursor materials must not exceed 0.01% (100 ppm) by weight. The amount of cadmium in Cd-free nanostructures is limited by the trace metal concentration in the precursor material. The trace metal (including cadmium) concentration in Cd-free nanostructure precursor materials can be measured by inductively coupled plasma mass spectrometry (ICP-MS) analysis and is at the parts per billion (ppb) level. In some embodiments, "cadmium-free" nanostructures contain less than about 50 ppm, less than about 20 ppm, less than about 10 ppm, or less than about 1 ppm cadmium.

[0165]

[0168] In some embodiments, the core is a III-V nanostructure. In some embodiments, the core is a III-V nanocrystal selected from the group consisting of BN, BP, BAs, BSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb. In some embodiments, the core is an InP nanocrystal. In some embodiments, the core is a ZnSe nanocrystal.

[0166]

[0169] The synthesis of Group III-V nanostructures is described in U.S. Patent Nos. 5,505,928, 6,306,736, 6,576,291, 6,788,453, 6,821,337, 7,138,098, 7,557,028, 7,645,397, 8,062,967, and 8,282,412, and U.S. Patent Application Publication No. 2015 / 0236195. Synthesis of Group III-V nanostructures has also been described in Wells, R.L., et al., "The use of tris(trimethylsilyl)arsine to prepare gallium arsenide and indium arsenide," Chem. Mater. 1:4-6 (1989) and in Guzelian, A.A., et al., "Colloidal chemical synthesis and characterization of InAs nanocrystal quantum dots," Appl. Phys. Lett. 69: 1432-1434 (1996).

[0167]

[0170] The synthesis of InP-based nanostructures is described, for example, in Xie, R., et al., “Colloidal InP nanocrystals as efficient emitters covering blue to near-infrared,” J. Am. Chem. Soc. 129:15432-15433 (2007); Micic, O. I., et al., “Core-shell quantum dots of lattice-matched ZnCdSe2 shells on InP cores: Experiment and theory,” J. Phys. Chem. B 104:12149-12156 (2000); Liu, Z., et al., “Coreduction colloidal synthesis of III-V nanocrystals: The case of InP,” Angew. Chem. Int. Ed. Engl. 47:3540-3542 (2008); Li, L., et al., “Economic synthesis of high quality InP nanocrystals using calcium phosphide as the phosphorus precursor,” Chem. Mater. 20:2621-2623 (2008); D. Battaglia and X. Peng, “Formation of high quality InP and InAs nanocrystals in a noncoordinating solvent,” Nano Letters 2:1027-1030 (2002); Kim, S., et al., “Highly luminescent InP / GaP / ZnS nanocrystals and their application to white light-emitting diodes,” J. Am. Chem. Soc. 134:3804-3809 (2012); Nann, T., et al., “Water splitting by visible light: A nanophotocathode for hydrogen production,” Angew. Chem. Int. Ed.49:1574-1577(2010);Borchert,H.,et al.,“Investigation of ZnS passivated InP nanocrystals by XPS,”Nano Letters 2:151-154(2002);L.Li and P.Reiss,“One-pot synthesis of highly luminescent InP / ZnS nanocrystals without precursor injection,”J.Am.Chem.Soc.130:11588-11589(2008);Hussain,S.,et al.“One-pot fabrication of high-quality InP / ZnS(core / shell)quantum dots and their application to cellular imaging,”Chemphyschem.10:1466-1470 (2009);Xu,S.,et al.,“Rapid synthesis of high-quality InP nanocrystals,”J.Am.Chem.Soc.128:1054-1055(2006);Micic,O.I.,et al.,“Size-dependent spectroscopy of InP quantum dots,”J.Phys.Chem.B 101:4904-4912(1997);Haubold,S.,et al.,“Strongly luminescent InP / ZnS core-shell nanoparticles,”Chemphyschem.5:331-334(2001);CrosGagneux,A.,et al.,“Surface chemistry of InP quantum dots:A comprehensive study,”J.Am.Chem.Soc.132:18147-18157(2010);Micic,O.I.,et al.,“Synthesis and characterization of InP,GaP,and GaInP2quantum dots,”J. Phys.Chem.99:7754-7759(1995);Guzelian,A.A.,et al.,“Synthesis of size-selected,surface-passivated InP nanocrystals,”J. Phys.Chem.100:7212-7219(1996);Lucey,DW,et al.,“Monodispersed InP quantum dots prepared by colloidal chemistry in a non-coordinating solvent,”Chem.Mater.17:3754-3762(2005);Lim,J.,et al.,“InP@ZnSeS,core@composition gradient shell quantum dots with enhanced stability,”Chem.Mater.23:4459-4463(2011);andZan,F.,et al.,“Experimental studies on blinking behavior of single InP / ZnS quantum dots:Effects of synthetic conditions and UV irradiation,”J.Phys.Chem.C 116:394-3950(2012).

[0168]

[0171] In some embodiments, the core is doped. In some embodiments, the dopant of the nanocrystalline core comprises one or more metals, such as transition metals. In some embodiments, the dopant is a transition metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and combinations thereof. In some embodiments, the dopant comprises a non-metal. In some embodiments, the dopant is ZnS, ZnSe, ZnTe, CdSe, CdS, CdTe, HgS, HgSe, HgTe, CuInS2, CuInSe2, AlN, AlP, AlAs, GaN, GaP, or GaAs.

[0169]

[0172] Inorganic shell coatings on nanostructures are a versatile method for tailoring their electronic structure. Furthermore, the deposition of inorganic shells and passivation of surface defects can produce more robust particles. Ziegler, J., et al., Adv. Mater. 20:4068-4073 (2008). For example, a shell of a wider bandgap semiconductor, such as ZnS, can be deposited on a core with a narrow bandgap, such as CdSe or InP, resulting in a structure in which excitons are confined within the core. This approach increases the probability of radiative recombination, enabling the synthesis of highly efficient quantum dots with thin shell coatings and quantum yields approaching unity.

[0170]

[0173] In some embodiments, the nanostructure comprises a core and at least one shell. In some embodiments, the nanostructure comprises a core and at least two shells. The shell can, for example, enhance the quantum yield and / or stability of the nanostructure. In some embodiments, the core and shell comprise different materials. In some embodiments, the nanostructure comprises shells of different shell materials.

[0171]

[0174] Exemplary materials for fabricating the shell include, but are not limited to, Si, Ge, Sn, Se, Te, B, C (including diamond), P, Co, Au, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, SiN, GeN, AlO, AlCO, and combinations thereof.

[0172]

[0175] In some embodiments, the shell is a mixture of at least two of a zinc source, a selenium source, a sulfur source, a tellurium source, and a cadmium source. In some embodiments, the shell is a mixture of two of a zinc source, a selenium source, a sulfur source, a tellurium source, and a cadmium source. In some embodiments, the shell is a mixture of three of a zinc source, a selenium source, a sulfur source, a tellurium source, and a cadmium source. In some embodiments, the shell is a mixture of zinc and sulfur; zinc and selenium; zinc, sulfur, and selenium; zinc and tellurium; zinc, tellurium, and sulfur; zinc, tellurium, and selenium; zinc, cadmium, and sulfur; zinc, cadmium, and selenium; cadmium and sulfur; cadmium and selenium; cadmium and zinc; cadmium, zinc, and sulfur; cadmium, zinc, and selenium; or a mixture of cadmium, zinc, sulfur, and selenium. In some embodiments, the shell is a mixture of zinc and selenium, hi some embodiments, the shell is a mixture of zinc and sulfur.

[0173]

[0176] Exemplary core / shell luminescent nanostructures include, but are not limited to, CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, and CdTe / ZnS (referred to as core / shell). The synthesis of core / shell nanostructures is disclosed in U.S. Patent No. 9,169,435.

[0174]

[0177] In some embodiments, the nanostructure comprises a core and at least one shell. In some embodiments, one shell is a mixture of zinc and selenium. In some embodiments, the nanostructure comprises a ZnS core and a ZnSe shell.

[0175]

[0178] In some embodiments, the nanostructure comprises a core and at least two shells. In some embodiments, one shell is a mixture of zinc and selenium and the other shell is a mixture of zinc and sulfur. In some embodiments, the nanostructure comprises an InP core, a ZnSe shell, and a ZnS shell.

[0176]

[0179] The luminescent nanocrystals can be made from oxygen-impermeable materials, thereby simplifying the oxygen barrier requirements and photostabilizing the quantum dots in the quantum dot film layer. In exemplary embodiments, the luminescent nanocrystals are coated with one or more organic polymeric ligand materials and dispersed in an organic polymer matrix containing one or more matrix materials. The luminescent nanocrystals can be further coated with one or more inorganic layers containing one or more materials such as silicon oxide, aluminum oxide, or titanium oxide (e.g., SiO2, SiO3, TiO2, or Al2O3) to encapsulate the quantum dots.

[0177] First Ligand

[0180] In some embodiments, the nanostructures include a ligand attached to their surface. In some embodiments, the nanostructures include a coating layer containing the ligand to protect the nanostructures from external moisture and oxidation, control aggregation, and enable dispersion of the nanostructures in a matrix material. Suitable first ligands include those disclosed in U.S. Patent Nos. 6,949,206; 7,267,875; 7,374,807; 7,572,393; 7,645,397; and 8,563,133, as well as U.S. Patent Application Publication Nos. 2008 / 0237540; 2008 / 0281010; and 2010 / 0110728.

[0178]

[0181] In some embodiments, the nanostructures comprise multi-part ligand structures, such as the three-part ligand structures disclosed in U.S. Patent Application Publication No. 2008 / 237540, in which head, tail, and center / body groups are independently engineered and optimized for their specific functions, and then combined into a complete, ideally functional surface ligand.

[0179]

[0182] In some embodiments, the first ligand comprises one or more organic polymeric ligands. Suitable ligands are those that encapsulate the quantum dots with high efficiency and strong binding in a low oxygen permeability capsule; precipitate or segregate as domains within the matrix material to form a discontinuous two-phase or multi-phase matrix; are advantageously dispersed throughout the matrix material; and are commercially available or can be easily formulated from commercially available materials.

[0180]

[0183] In some embodiments, the first ligand comprises a carboxy, thiol, phosphine, or phosphine oxide group.

[0181]

[0184] In some embodiments, the first ligand comprises a carboxy group. In some embodiments, the first ligand comprises a carboxylic acid group. In some embodiments, the first ligand comprises a carboxylic acid group, and the carboxylic acid is caprylic acid, capric acid, lauric acid, myristic acid, or palmitic acid. In some embodiments, the first ligand is a carboxylate. In some embodiments, the first ligand comprises a carboxylate, and the carboxylate is a carboxyalkyl.

[0182]

[0185] In some embodiments, the first ligand comprises a phosphine group, hi some embodiments, the first ligand comprises a phosphine group, and the phosphine group is triphenylphosphine, tributylphosphine, trihexylphosphine, trioctylphosphine (TOP), or tridecylphosphine.

[0183]

[0186] In some embodiments, the first ligand comprises a phosphine oxide group, hi some embodiments, the first ligand comprises a phosphine oxide group, and the phosphine oxide is triphenylphosphine oxide, tributylphosphine oxide, trihexylphosphine oxide, trioctylphosphine oxide (TOPO), or tridecylphosphine oxide.

[0184] Acceptor site

[0187] In some embodiments, each acceptor moiety is independently, for each occurrence, a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents. In some embodiments, each acceptor moiety is covalently bonded to a functional group. In some embodiments, each acceptor moiety is covalently bonded to a -COH moiety. In some embodiments, each acceptor moiety is covalently bonded to a donor moiety.

[0185]

[0188] In some embodiments, the acceptor moiety (A) is a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms substituted with at least one cyano, ketone, ester, amide, aldehyde, sulfone, sulfoxide, or phosphine oxide.

[0186]

[0189] In some embodiments, the acceptor moiety (A) is a pyridine, pyrimidine, pyrazine, triazine, triazole, or oxadiazole, optionally substituted with one or more substituents.

[0187]

[0190] In some embodiments, the acceptor moiety (A) has Formula V: [ka] containing a radical of In the above formula, A1 to A6 independently contain C or N, and at least one of A1 to A6 is N; R1, R2, and R3 are each independently hydrogen, C1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0188]

[0191] In some embodiments, A3 and A5 of formula V are C, R1 and R4 are phenyl, and the acceptor moiety (A) is formula VI: [ka] containing a radical of a compound of In the above formula, R4 and R5 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0189]

[0192] In some embodiments, in Formula V, A1, A3, and A5 are C, R1-R3 are phenyl, and the acceptor moiety (A) is represented by Formula VII: [ka] containing a radical of a compound of the formula In the above formula, R6, R7, and R8 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0190]

[0193] In some embodiments, in Formula V, A4 and A5 together with the carbon atoms to which they are attached form a 6-membered aromatic or heteroaromatic ring, and the acceptor moiety (A) is represented by Formula VIII: [ka] containing a radical of a compound of the formula In the above formula, A7 to A 10 independently comprises C or N; R9 is hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0191]

[0194] In some embodiments, in the compound of Formula VIII, A2 and A6 are N, and A1, A3, A7 to A 10 is C and R9 is H. In some embodiments, in the compound of Formula VIII, A3 and A6 are N and A1, A2, and A7-A 10 is C and R9 is H.

[0192]

[0195] In some embodiments, the acceptor moiety (A) has the formula IX: [ka] containing a radical of a compound of the formula In the above formula, A 11 ~A 14 independently contains C or N, and A 11 ~A 14at least one of is N; X1 is O, S, or NR 12 and; R 10 and R 11 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 12 is hydrogen, C 1~10 Alkyl, C 6~18 It is aryl or heteroaryl.

[0193]

[0196] In some embodiments, the acceptor moiety (A) has the formula X: [ka] containing a radical of a compound of the formula In the above formula, A 15 ~A 22 independently comprises C or N; X2 is O or S; R 13 , R 14 , and R 15 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0194]

[0197] In some embodiments, in the compound of formula X, A15 ~A 22 is C, X2 is O, and R 13 ~R 15 is H.

[0195]

[0198] In some embodiments, the acceptor moiety (A) has formula XI: [ka] containing a radical of a compound of the formula In the above formula, A 23 ~A 34 independently comprises C or N; R 16 , R 17 , and R 18 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0196]

[0199] In some embodiments, in the compound of formula XI, A 23 is N and A 24 ~A 34 is C, and R 16 ~R 18 is H. In some embodiments, in the compound of formula XI, A 23 and A 34 is N and A 24 ~A 33 is C, and R 16 ~R 18 is H.

[0197]

[0200] In some embodiments, the acceptor moiety (A) is represented by Formula XII: [ka] containing a radical of a compound of the formula In the above formula, A 35 ~A 38 independently comprises C or N; X3 is O, S, or NR 21 and; R 19 and R 20 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 21 is hydrogen, C 1~10 Alkyl, C 6~18 It is aryl or heteroaryl.

[0198]

[0201] In some embodiments, in the compound of Formula XII, A 35 ~A 38 is C and X3 is NR 21 and R 19 and R 20 is H, and NR 21 is phenyl. In some embodiments, in the compound of formula XII, A 35 ~A 38 is C and X3 is NR 21 and R 19 is hydrogen and R 20 and R 21 is phenyl.

[0199]

[0202] In some embodiments, the acceptor moiety (A) has the formula XIII: [ka] containing a radical of a compound of the formula In the above formula, A 39 and A40 independently comprises C or N; X4 to X7 are independently C, O, S, N, or NR 23 and at least one of X4 to X7 is NR 23 and; R 22 But hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, SO2H, NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 23 is hydrogen, C 1~10 Alkyl, C 6~18 It is aryl or heteroaryl.

[0200]

[0203] In some embodiments, the acceptor moiety (A) has the formula XIV: [ka] containing a radical of a compound of the formula In the above formula, A 41 ~A 53 independently contains C or N.

[0201]

[0204] In some embodiments, A 41 , A 43 , A 45 , A 47 , A 49 , A 51 , and A 53 contains N and A 42 , A 44 , A 46 , A 48 , A 50 , and A 52 contains C.

[0202]

[0205] In some embodiments, the acceptor moiety (A) has the formula XV: [ka] containing a radical of a compound of the formula In the above formula, X8 is C(O) or S(O)2; X9 is CR 26 R 27 , C(O), or S(O)2; R 24 and R 25 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 26 and R 27 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0203]

[0206] In some embodiments, X8 is C(O) and R 24 and R 25 is H. In some embodiments, X is S(O) and R 24 and R 25 is H.

[0204]

[0207] In some embodiments, the acceptor moiety (A) has the formula XVI: [ka] containing a radical of a compound of the formula In the above formula, A 54 ~A 61 independently comprises C or N; X 10 is CR 30 R 31 , S, O, or S(O)2; R 28 and R 29 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 30 and R 31 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0205]

[0208] In some embodiments, the acceptor moiety (A) is represented by Formula XVII: [ka] containing a radical of a compound of the formula In the above formula, R 32 is -SO2-(C 6~18 aryl), -CN, -C(O)-(C 6~18 aryl), -C(O)-(C 6~18 aryl)-C(O)-(C 6~18 aryl), -SO2-(C6~18 aryl)-SO2-(C 6~18 aryl), or -B-(C 6~18 aryl)2; R 33 is hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 34 is hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0206]

[0209] In some embodiments, each acceptor moiety is a radical of a compound selected from Table 1.

[0207] [Table 1]

[0208] [Table 2]

[0209] [Table 3]

[0210] [Table 4]

[0211] [Table 5]

[0212] [Table 6]

[0213] [Table 7]

[0214] [Table 8]

[0215] [Table 9]

[0216] [Table 10]

[0217] In some embodiments, the acceptor moiety is commercially available. In some embodiments, the acceptor moiety is prepared using methods known to those skilled in the art. See Im, Y., et al., Chemistry of Materials 29:1946-1963 (2017).

[0218] Donor site In some embodiments, the donor moiety is, independently for each occurrence, a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents. In some embodiments, each donor moiety is covalently bonded to at least one functional group. In some embodiments, each donor moiety is covalently bonded to at least one —COH. In some embodiments, each donor moiety is covalently bonded to at least one acceptor moiety.

[0219] In some embodiments, each donor moiety (D) is a carbazole, benzofurocarbazole, thienocarbazole, indolocarbazole, bicarbazole, amine, diamine, acridan, phenoxazine, phenothiazine, or phenazine, optionally substituted with one or more substituents.

[0220] In some embodiments, the donor moiety (D) has Formula XVIII: [ka] containing a radical of a compound of the formula In the above formula, D1 to D8 independently contain C or N; X 11 But O, S, NR 37 , C.R. 38 R 39 , and S.R. 40 R 41 selected from the group consisting of: R 35 and R 36 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 37 , R 38 , R 39 , R 40 , and R 41 are independently hydrogen, C 1~10 Alkyl, C 6~18 It is aryl or heteroaryl.

[0221] In some embodiments, the donor moiety (D) has the formula XIX: [ka] containing a radical of a compound of the formula In the above formula, D9 to D 16 independently comprises C or N; R 42 and R 45 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0222] In some embodiments, the donor moiety (D) has the formula XX: [ka] containing a radical of a compound of the formula In the above formula, D 17 ~D 24 independently comprises C or N; X 12 But O, S, NR 48 , C.R. 49 R 50 , and S.R. 51 R 52 selected from the group consisting of: R 46 and R 47 are independently hydrogen, C1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 48 , R 49 , R 50 , R 51 , and R 52 are independently hydrogen, C 1~10 Alkyl, C 6~18 It is aryl or heteroaryl.

[0223] In some embodiments, the donor moiety (D) has formula XXI: [ka] containing a radical of a compound of the formula In the above formula, D 25 ~D 32 independently comprises C or N; X 12 But O, S, NR 55 , C.R. 56 R 57 , and S.R. 58 R 59 selected from the group consisting of: R 53 and R 54 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 55 , R 56 , R57 , R 58 , and R 59 are independently hydrogen, C 1~10 Alkyl, C 6~18 It is aryl or heteroaryl.

[0224] In some embodiments, the donor moiety (D) has Formula XXII: [ka] containing a radical of a compound of the formula In the above formula, D 33 ~D 42 independently comprises C or N; R 60 and R 61 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 It is a haloaryl.

[0225]

[0218] In some embodiments, each donor moiety is a radical of a compound selected from Table 2, which donor moiety can be optionally substituted.

[0226] [Table 11]

[0227] [Table 12]

[0228] [Table 13]

[0229] [Table 14]

[0230] [Table 15]

[0231] [Table 16]

[0232] [Table 17]

[0233] [Table 18]

[0234] In some embodiments, the donor site is commercially available. In some embodiments, the donor site is prepared using methods known to those skilled in the art. See Im, Y., et al., Chemistry of Materials 29:1946-1963 (2017).

[0235] Donor-Acceptor Ligands In some embodiments, the donor-acceptor ligand comprises at least one functional group (FG) capable of binding to the nanocrystal surface.

[0236] In some embodiments, the donor-acceptor ligand includes at least one functional group (FG) attached to a terminus of the donor-acceptor ligand. In some embodiments, the at least one functional group is —OH, —SH, —NH, —COH, —P(O)(OH), —P(O)OH, or —SOH. In some embodiments, the at least one functional group is —COH.

[0237] In some embodiments, the donor-acceptor ligand has Formula I: D d -A a -FG f (I) having the structure In the above formula, FG is -OH, -SH, -NH2, -CO2H, -P(O)(OH)2, -P(O)OH, or -SO3H; D is a donor moiety that comprises, independently for each occurrence, a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; A is an acceptor moiety comprising a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer of 1 to 4.

[0238] In some embodiments, the donor-acceptor ligand has Formula II: A a -D d -FG f (II) having the structure In the above formula, FG is -OH, -SH, -NH2, -CO2H, -P(O)(OH)2, -P(O)OH, or -SO3H; A is an acceptor moiety that independently for each occurrence comprises a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; D is a donor moiety comprising a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer of 1 to 4.

[0239] In some embodiments, FG is —CO 2 H in Formula I and the donor-acceptor ligand is —CO 2 H in Formula III: [ka] having the structure wherein D is a donor moiety that independently for each occurrence comprises a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; A is an acceptor moiety comprising a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer of 1 to 4.

[0240] In some embodiments, FG is —CO 2 H in Formula I and the donor-acceptor ligand is —CO 2 H in Formula IV: [ka] having the structure wherein A is an acceptor moiety that independently for each occurrence comprises a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; D is a donor moiety comprising a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer of 1 to 4.

[0241] In some embodiments, the donor-acceptor ligand has Formula I or Formula II: D d -A a -FG f (I) or A a -D d -FG f (II) having the structure In the above formula, FG is -OH, -SH, -NH2, -CO2H, -P(O)(OH)2, -P(O)OH, or -SO3H; A is, (i) A compound of formula V: [ka] (Wherein, A1 to A6 independently contain C or N, and at least one of A1 to A6 is N; R1, R2, and R3 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (ii) A compound of formula IX: [ka] (In the formula, A 11 ~A 14 independently contain C or N, and A 11 ~A 14at least one of is N; X1 is O, S, or NR 12 and; R 10 and R 11 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 12 But hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (iii) A compound of formula X: [ka] (In the formula, A 15 ~A 22 independently comprises C or N; X2 is O or S; R 13 , R 14 , and R 15 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (iv) A compound of formula XI: [ka] (In the formula, A 23 ~A 34 independently comprises C or N; R 16 , R 17 , and R 18 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (v) A compound of formula XII: [ka] (In the formula, A 35 ~A 38 independently comprises C or N; X3 is O, S, or NR 21 and; R 19 and R 20 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 21 is hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (vi) Compound of formula XIII: [ka] (In the formula, A 39 and A 40 independently comprises C or N; X4 to X7 are independently C, O, S, N, or NR 23and at least one of X4 to X7 is NR 23 and; R 22 But hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 23 is hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (vii) Compound of formula XIV: [ka] (In the formula, A 41 ~A 53 independently contain C or N); (viii) Compound of formula XV: [ka] (Wherein X8 is C(O) or S(O)2; X9 is CR 26 R 27 , C(O), or S(O)2; R 24 and R 25 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 26 and R 27are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (ix) Compound of formula XVI: [ka] (In the formula, A 54 ~A 61 independently comprises C or N; X 10 is CR 30 R 31 , S, O, or S(O)2; R 28 and R 29 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 30 and R 31 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (x) A compound of formula XVII: [ka] (In the formula, R 32 is -SO2-(C 6~18 aryl), -CN, -C(O)-(C 6~18 aryl), -C(O)-(C 6~18 aryl)-C(O)-(C 6~18 aryl), -SO2-(C 6~18 aryl)-SO2-(C 6~18 aryl), or -B-(C 6~18 aryl)2; R 33 is hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 34 is hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl) is an acceptor moiety containing a radical of D is, (i') Compound of Formula XVIII: [ka] (Wherein, D1 to D8 independently contain C or N; X 11 But O, S, NR 37 , C.R. 38 R 39, and S.R. 40 R 41 selected from the group consisting of: R 35 and R 36 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 37 , R 38 , R 39 , R 40 , and R 41 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (ii') Compound of formula XIX: [ka] (In the formula, D9~D 16 independently comprises C or N; R 42 and R 45 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (iii') Compound of formula XX: [ka] (In the formula, D 17 ~D 24 independently comprises C or N; X 12 But O, S, NR 48 , C.R. 49 R 50 , and S.R. 51 R 52 selected from the group consisting of: R 46 and R 47 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 48 , R 49 , R 50 , R 51 , and R 52 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (iv') Compound of formula XXI: [ka] (In the formula, D 25 ~D 32 independently comprises C or N; X 12 But O, S, NR 55 , C.R. 56 R 57 , and S.R. 58 R 59 selected from the group consisting of: R 53 and R 54 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 55 , R 56 , R 57 , R 58 , and R 59 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (v') Compound of Formula XXII: [ka] (In the formula, D 33 ~D 42 independently comprises C or N; R 60 and R 61 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl) is a donor moiety containing a radical of a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer of 1 to 4.

[0242]

[0227] In some embodiments, the donor-acceptor ligand is selected from Table 3, where the donor site may be optionally substituted and the acceptor site may be optionally substituted.

[0243] [Table 19]

[0244] [Table 20]

[0245] Ligand exchange In some embodiments, the present invention relates to a method of exchanging ligands on nanostructures. In some embodiments, a first ligand on a nanostructure dot is exchanged with at least one donor-acceptor ligand. At least one functional group of the donor-acceptor ligand replaces a negative hydrophobic ligand on the nanostructure, resulting in stable anchoring of the ligand on the nanocrystal surface. In some embodiments, the nanostructure is a quantum dot. In some embodiments, at least one donor-acceptor ligand is a bipolar ligand. In some embodiments, at least one donor-acceptor ligand is a TADF ligand.

[0246] In some embodiments, the present disclosure relates to a method of replacing a first ligand on a nanostructure with a second ligand. In some embodiments, the second ligand is a donor-acceptor ligand. In some embodiments, the nanostructure is a quantum dot.

[0247] In some embodiments, the present disclosure provides a method of replacing a first ligand on a nanostructure with a second ligand, the method comprising: The method includes mixing a reaction mixture containing a population of nanostructures having a first ligand bound to the nanostructures and at least one donor-acceptor ligand, the second ligand, such that the second ligand displaces the first ligand and binds to the nanostructures.

[0248] In some embodiments, the combined reaction mixture is substantially solvent-free. In some embodiments, the combined reaction mixture is solvent-free. As used herein, the term "substantially solvent-free" contemplates that the combined reaction mixture contains less than 2% by weight of solvent. In some embodiments, the combined reaction mixture contains less than 1% by weight, less than 0.5% by weight, or less than 0.1% by weight of solvent. Solvent ligand exchange can be performed when the second ligand is a donor-acceptor ligand, and the donor-acceptor ligand is T g less than 100° C. and a viscosity of less than about 1000 cSt (see U.S. Pat. No. 9,005,480, which is incorporated herein by reference in its entirety).

[0249]

[0232] In some embodiments, the nanostructures are quantum dots.

[0250] In some embodiments, the first ligand is covalently attached to the nanostructure. In some embodiments, the first ligand is non-covalently attached to the nanostructure.

[0251] In some embodiments, the second ligand becomes covalently attached to the nanostructure. In some embodiments, the second ligand becomes non-covalently attached to the nanostructure.

[0252] In some embodiments, the mixing is carried out at a temperature of about 0 to about 200°C, about 0 to about 150°C, about 0 to about 100°C, about 0 to about 80°C, about 20 to about 200°C, about 20 to about 150°C, about 20 to about 100°C, about 20 to about 80°C, about 50 to about 200°C, about 50 to about 150°C, about 50 to about 100°C, about 50 to about 80°C, about 80 to about 200°C, about 80 to about 150°C, about 80 to about 100°C, about 100 to about 200°C, about 100 to about 150°C, or about 150 to about 200°C. In some embodiments, the mixing is carried out at a temperature of about 50 to about 100°C. In some embodiments, the mixing is carried out at a temperature of about 80°C.

[0253] In some embodiments, the mixing may be performed for about 1 minute to about 6 hours, about 1 minute to about 2 hours, about 1 minute to about 1 hour, about 1 minute to about 40 minutes, about 1 minute to about 30 minutes, about 1 minute to about 20 minutes, about 1 minute to about 10 minutes, about 10 minutes to about 6 hours, about 10 minutes to about 2 hours, about 10 minutes to about 1 hour, about 10 minutes to about 40 minutes, about 10 minutes to about 30 minutes, about 10 minutes to about 20 minutes, about 20 minutes to about 6 hours, about 2 The mixing may be performed over a period of 0 minutes to about 2 hours, about 20 minutes to about 1 hour, about 20 minutes to about 40 minutes, about 20 minutes to about 30 minutes, about 30 minutes to about 6 hours, about 30 minutes to about 2 hours, about 30 minutes to about 1 hour, about 30 minutes to about 40 minutes, about 40 minutes to about 6 hours, about 40 minutes to about 2 hours, about 40 minutes to about 1 hour, about 1 hour to about 6 hours, about 1 hour to about 2 hours, or about 2 hours to about 6 hours. In some embodiments, the mixing is performed over a period of about 40 minutes to about 2 hours. In some embodiments, the mixing is performed over a period of about 1 hour.

[0254] In some embodiments, the reaction mixture further comprises a solvent. In some embodiments, the solvent is selected from the group consisting of chloroform, acetone, butanone, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, methyl isobutyl ketone, monomethyl ether glycol esters, γ-butyrolactone, methyl acetate-3-ethyl ether, butyl carbitol, butyl carbitol acetate, propanediol monomethyl ether, propanediol monomethyl ether acetate, cyclohexane, toluene, xylene, isopropyl alcohol, and combinations thereof. In some embodiments, the solvent is toluene.

[0255] The percentage of the first ligand that is displaced by the donor-acceptor ligand is 1This can be measured by H NMR or Fourier transform infrared spectroscopy (FTIR). In some embodiments, the mole percent of the first ligand replaced by the donor-acceptor ligand is about 20 to about 100%, about 20 to about 80%, about 20 to about 60%, about 20 to about 40%, about 25 to about 100%, about 25 to about 80%, about 25 to about 60%, about 25 to about 40%, about 30 to about 100%, about 30 to about 80%, about 30 to about 60%, about 30 to about 40%, about 40 to about 100%, about 40 to about 80%, about 40 to about 60%, about 60 to about 100%, about 60 to about 80%, or about 80 to about 100%.

[0256] The percentage of donor-acceptor ligands bound to nanostructures in a population of nanostructures is 1 The bound ligand can be measured by 1 H NMR and calculated using (bound donor-acceptor ligand) / (bound + free donor-acceptor ligand).

[0257]

[0240] In some embodiments, the molar percentage of donor-acceptor ligands bound to the nanostructure is about 20 to about 100%, about 20 to about 100%, about 20 to about 80%, about 20 to about 60%, about 20 to about 40%, about 25 to about 100%, about 25 to about 80%, about 25 to about 60%, about 25 to about 40%, about 30 to about 100%, about 30 to about 80%, about 30 to about 60%, about 30 to about 40%, about 40 to about 100%, about 40 to about 80%, about 40 to about 60%, about 60 to about 100%, about 60 to about 80%, or about 80 to about 100%.

[0258] Nanostructure composition

[0241] In some embodiments, the present disclosure provides (a) at least one population of nanostructures; and (b) at least one donor-acceptor ligand; wherein the donor-acceptor ligand comprises at least one terminal functional group, and the at least one terminal functional group is attached to a surface of the nanostructure.

[0259] In some embodiments, the nanostructure composition further comprises: (c) comprises at least one organic resin.

[0260] In some embodiments, the present disclosure provides: (a) at least one population of nanostructures; and (b) at least one donor-acceptor ligand bound to the surface of the nanostructure; A nanostructure composition comprising: The donor-acceptor ligand is: (i) a donor-acceptor ligand of Formula I or Formula II: D d -A a -FG f (I) or A a -D d -FG f (II) wherein FG is -OH, -SH, -NH, -COH, -P(O)(OH), -P(O)OH, or -SOH; D is a donor moiety comprising a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; A is an acceptor moiety that independently for each occurrence comprises a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer from 1 to 4; or (ii) any combination thereof; The present invention provides a nanostructure composition comprising:

[0261] In some embodiments, the nanostructure further comprises: (c) comprises at least one organic resin.

[0262] In some embodiments, the present disclosure provides: (a) at least one population of nanostructures, the nanostructures comprising ligands bound to the nanostructures; and (b) at least one donor-acceptor ligand bound to the surface of the nanostructure; A nanostructure composition comprising: The donor-acceptor ligand is: (i) a donor-acceptor ligand of formula III or formula IV: [ka] wherein D is a donor moiety that comprises, independently for each occurrence, a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; A is an acceptor moiety comprising a monocyclic or fused polycyclic aryl or heteroaryl containing 5 to 20 atoms, optionally substituted with one or more substituents; a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer from 1 to 4; or (ii) any combination thereof; The present invention provides a nanostructure composition comprising:

[0263] In some embodiments, the nanostructure further comprises: (c) comprises at least one organic resin.

[0264]

[0247] In some embodiments, the present disclosure provides (a) at least one population of nanostructures, the nanostructures comprising ligands bound to the nanostructures; and (b) at least one donor-acceptor ligand bound to the surface of the nanostructure; A nanostructure composition comprising: The donor-acceptor ligand is: (i) Formula I or Formula II: Dd -A a -FG f (I) or A a -D d -FG f (II) having the structure In the above formula, FG is -OH, -SH, -NH2, -CO2H, -P(O)(OH)2, -P(O)OH, or -SO3H; A is, (i) A compound of formula V: [ka] (Wherein, A1 to A6 independently contain C or N, and at least one of A1 to A6 is N; R1, R2, and R3 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (ii) A compound of formula IX: [ka] (In the formula, A 11 ~A 14 independently contains C or N, and A 11 ~A 14 at least one of is N; X1 is O, S, or NR 12 and; R 10 and R 11 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 12 is hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (iii) A compound of formula X: [ka] (In the formula, A 15 ~A 22 independently comprises C or N; X2 is O or S; R 13 , R 14 , and R 15 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (iv) A compound of formula XI: [ka] (In the formula, A 23 ~A 34 independently comprises C or N; R 16 , R 17 , and R 18 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C6~18 haloaryl); or (v) A compound of formula XII: [ka] (In the formula, A 35 ~A 38 independently comprises C or N; X3 is O, S, or NR 21 and; R 19 and R 20 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 21 is hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (vi) Compound of formula XIII: [ka] (In the formula, A 39 and A 40 independently comprises C or N; X4 to X7 are independently C, O, S, N, or NR 23 and at least one of X4 to X7 is NR 23 and; R 22 But hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, NO2, -CN, halogen, cycloalkyl, or C6~18 is a haloaryl; R 23 is hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (vii) Compound of formula XIV: [ka] (In the formula, A 41 ~A 53 independently contain C or N); (viii) Compound of formula XV: [ka] (Wherein X8 is C(O) or S(O)2; X9 is CR 26 R 27 , C(O), or S(O)2; R 24 and R 25 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 26 and R 27 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (ix) Compound of formula XVI: [ka] (In the formula, A 54 ~A 61 independently comprises C or N; X 10 is CR 30 R 31 , S, O, or S(O)2; R 28 and R 29 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 30 and R 31 are each independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (x) A compound of formula XVII: [ka] (In the formula, R 32 is -SO2-(C 6~18 aryl), -CN, -C(O)-(C 6~18 aryl), -C(O)-(C 6~18 aryl)-C(O)-(C 6~18 aryl), -SO2-(C 6~18 aryl)-SO2-(C 6~18 aryl), or -B-(C 6~18aryl)2; R 33 is hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 34 is hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl) is an acceptor moiety containing a radical of D is, (i') Compound of Formula XVIII: [ka] (Wherein, D1 to D8 independently contain C or N; X 11 But O, S, NR 37 , C.R. 38 R 39 , and S.R. 40 R 41 selected from the group consisting of: R 35 and R 36 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 37 , R 38 , R 39 , R 40 , and R 41 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (ii') Compound of formula XIX: [ka] (In the formula, D9~D 16 independently comprises C or N; R 42 ~R 45 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl); or (iii') Compound of formula XX: [ka] (In the formula, D 17 ~D 24 independently comprises C or N; X 12 But O, S, NR 48 , C.R. 49 R 50 , and S.R. 51 R 52 selected from the group consisting of: R 46 and R 47 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 48 , R 49 , R 50 , R 51 , and R 52 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (iv') Compound of formula XXI: [ka] (In the formula, D 25 ~D 32 independently comprises C or N; X 12 But O, S, NR 55 , C.R. 56 R 57 , and S.R. 58 R 59 selected from the group consisting of: R 53 and R 54 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 is a haloaryl; R 55 , R 56 , R 57 , R 58 , and R 59 are independently hydrogen, C 1~10 Alkyl, C 6~18 aryl, or heteroaryl; or (v') Compound of Formula XXII: [ka] (In the formula, D 33 ~D 42 independently comprises C or N; R 60 and R 61 are independently hydrogen, C 1~10 Alkyl, C 2~10 Alkenyl, C 2~10 Alkynyl, C 6~18 Aryl, heteroaryl, C 1~10 Alkoxy, C 1~10 Haloalkyl, C(O)C 1~3 Haloalkyl, -SO2H, -NO2, -CN, halogen, cycloalkyl, or C 6~18 haloaryl) is a donor moiety containing a radical of a is an integer from 1 to 4; d is an integer from 1 to 4; f is an integer of 1 to 4.

[0265] In some embodiments, the nanostructure composition further comprises: (c) comprises at least one organic resin.

[0266] Nanostructured film layer

[0249] In some embodiments, the present invention provides a method for treating a cancer comprising: (a) at least one population of nanostructures, the nanostructures comprising a ligand bound to the nanostructures; (b) at least one donor-acceptor ligand bound to the nanostructure; The nanostructure film layer comprises:

[0267]

[0250] In some embodiments, the present invention provides a method for treating a cancer cell comprising: (a) at least one population of nanostructures, the nanostructures comprising a ligand bound to the nanostructures; (b) at least one donor-acceptor ligand bound to the nanostructure; and (c) at least one organic resin The nanostructure film layer comprises:

[0268] In some embodiments, the nanostructures are quantum dots.

[0269]

[0252] In some embodiments, the nanostructure film layer is an emissive layer.

[0270] organic resin In some embodiments, the nanostructure composition further comprises at least one organic resin.

[0271] In some embodiments, the nanostructure composition comprises: (a) at least one population of nanostructures, wherein about 10 to about 100% of the nanostructures in the at least one population of nanostructures comprise donor-acceptor ligands bound to the nanostructures; and (b) at least one organic resin. In some embodiments, the nanostructures are quantum dots.

[0272]

[0255] In some embodiments, the organic resin is a thermosetting resin or an ultraviolet (UV) curable resin. In some embodiments, the organic resin is cured by a method that facilitates roll-to-roll processing.

[0273]

[0256] Thermosetting resins require curing to undergo an irreversible molecular crosslinking process that renders the resin infusible. In some embodiments, the thermosetting resin is an epoxy resin, a phenolic resin, a vinyl resin, a melamine resin, a urea resin, an unsaturated polyester resin, a polyurethane resin, an allylic resin, an acrylic resin, a polyamide resin, a polyamide-imide resin, a phenolamine condensation polymerization resin, a urea-melamine condensation polymerization resin, or a combination thereof.

[0274] In some embodiments, the thermosetting resin is an epoxy resin. Epoxy resins are easily cured with a wide range of chemicals without generating volatile substances or by-products. Epoxy resins are also compatible with most substrates and tend to wet surfaces easily. See Boyle, MA, et al., "Epoxy Resins," Composites, Vol. 21, ASM Handbook, pages 78-89 (2001).

[0275] In some embodiments, the organic resin is a silicone thermoset. In some embodiments, the silicone thermoset is OE6630A or OE6630B (Dow Corning Corporation, Auburn, MI).

[0276] In some embodiments, a thermal initiator is used. In some embodiments, the thermal initiator is AIBN [2,2'-azobis(2-methylpropionitrile)] or benzoyl peroxide.

[0277]

[0260] UV-curable resins are polymers that cure and rapidly harden when exposed to specific wavelengths of light. In some embodiments, the UV-curable resin is a resin having, as a functional group, a radical polymerizable group such as a (meth)acryloyloxy group, a vinyloxy group, a styryl group, or a vinyl group; or a cationically polymerizable group such as an epoxy group, a thioepoxy group, a vinyloxy group, or an oxetanyl group. In some embodiments, the UV-curable resin is a polyester resin, a polyether resin, a (meth)acrylic resin, an epoxy resin, a urethane resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, or a polythiolpolyene resin.

[0278] In some embodiments, the UV curable resin is selected from the group consisting of urethane acrylate, allyloxylated cyclohexyl diacrylate, bis(acryloxyethyl)hydroxyl isocyanurate, bis(acryloxyneopentyl glycol) adipate, bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, dicyclopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol di ...acrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1, Dipentaerythritol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, di(trimethylolpropane)tetraacrylate, ethylene glycol dimethacrylate, glycerol methacrylate, 1,6-hexanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol hydroxypivalate diacrylate, pentaerythritol triacrylate, pentaerythritol The polymer may be selected from the group consisting of litritol tetraacrylate, phosphate dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, tetrabromobisphenol A diacrylate, triethylene glycol divinyl ether, triglycerol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, tris(acryloxyethyl)isocyanurate, phosphate triacrylate, phosphate diacrylate, acrylic acid propargyl ester, vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinyl-terminated trifluoromethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane, monomethacryloyloxypropyl-terminated polydimethylsiloxane, monovinyl-terminated polydimethylsiloxane, monoallyl-monotrimethylsiloxy-terminated polyethylene oxide, and combinations thereof.

[0279] In some embodiments, the UV-curable resin is a mercapto-functional compound that can be crosslinked with an isocyanate, epoxy, or unsaturated compound under UV-curing conditions. In some embodiments, the polythiol is selected from the group consisting of pentaerythritol tetra(3-mercaptopropionate) (PETMP), trimethylolpropane tri(3-mercaptopropionate) (TMPMP), glycol di(3-mercaptopropionate) (GDMP), tris[25-(3-mercaptopropionyloxy)ethyl]isocyanurate (TEMPIC), di-pentaerythritol hexa(3-mercaptopropionate) (Di-PETMP), ethoxylated trimethylolpropane tri(3-mercaptopropionate) (ETTMP 1300 and ETTMP 700), polycaprolactone tetra(3-mercaptopropionate) (PCL4MP), and the like. 1350); pentaerythritol tetramercaptoacetate (PETMA); trimethylol-propane trimercaptoacetate (TMPMA); or glycol dimercaptoacetate (GDMA). These compounds are sold under the trade name THIOCURER® by Bruno Bock, Marschacht, Germany.

[0280] In some embodiments, the UV-curable resin is a polythiol. In some embodiments, the UV-curable resin is a polythiol selected from the group consisting of ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(thioglycolate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(thioglycolate), pentaerythritol tetrakis(3-mercaptopropionate) (PETMP), and combinations thereof. In some embodiments, the UV-curable resin is PETMP.

[0281] In some embodiments, the UV-curable resin is a thiol-ene formulation including polythiol and 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TTT). In some embodiments, the UV-curable resin is a thiol-ene formulation including PETMP and TTT.

[0282] In some embodiments, the UV-curable resin further comprises a photoinitiator. The photoinitiator initiates the crosslinking and / or curing reaction of the photosensitive material during exposure to light. In some embodiments, the photoinitiator is an acetophenone-type, benzoin-type, or thioxatenon-type photoinitiator.

[0283] In some embodiments, the photoinitiator is a vinyl acrylate-based resin. In some embodiments, the photoinitiator is MINS-311RM (Minuta Technology Co., Ltd., Korea).

[0284] In some embodiments, the photoinitiator is IRGACURE® 127, IRGACURE® 184, IRGACURE® 184D, IRGACURE® 2022, IRGACURE® 2100, IRGACURE® 250, IRGACURE® 270, IRGACURE® 2959, IRGACURE® 369, IRGACURE® 369EG, IRGACURE® 379, IRGACURE® 500, IRGACURE® 500E, IRGACURE® 500F, IRGACURE® 500G, IRGACURE® 500H ... In some embodiments, the photoinitiator is TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide) or MBF (methylbenzoyl formate).

[0285] In some embodiments, the weight percentage of the at least one organic resin in the nanostructure composition is about 5 to about 99%, about 5 to about 95%, about 5 to about 90%, about 5 to about 80%, about 5 to about 70%, about 5 to about 60%, about 5 to about 50%, about 5 to about 40%, about 5 to about 30%, about 5 to about 20%, about 5 to about 10%, about 10 to about 99%, about 10 to about 95 ... Approximately 90%, approximately 10 to approximately 80%, approximately 10 to approximately 70%, approximately 10 to approximately 60%, approximately 10 to approximately 50%, approximately 10 to approximately 40%, approximately 10 to approximately 30%, approximately 10 to approximately 20%, approximately 20 to approximately 99%, approximately 20 to approximately 95%, approximately 20 to approximately 90%, approximately 20 to approximately 80%, approximately 20 to approximately 70%, approximately 20 to approximately 60%, approximately 20 to approximately 50%, approximately 20 to approximately 40%, approximately 20 to approximately 30%, approximately 30 to approximately 99%, approximately 30 to about 95%, about 30 to about 90%, about 30 to about 80%, about 30 to about 70%, about 30 to about 60%, about 30 to about 50%, about 30 to about 40%, about 40 to about 99%, about 40 to about 95%, about 40 to about 90%, about 40 to about 80%, about 40 to about 70%, about 40 to about 60%, about 40 to about 50%, about 50 to about 99%, about 50 to about 95%, about 50 to about 90%, about 50 to about 80 %, about 50 to about 70%, about 50 to about 60%, about 60 to about 99%, about 60 to about 95%, about 60 to about 90%, about 60 to about 80%, about 60 to about 70%, about 70 to about 99%, about 70 to about 95%, about 70 to about 90%, about 70 to about 80%, about 80 to about 99%, about 80 to about 95%, about 80 to about 90%, about 90 to about 99%, about 90 to about 95%, or about 95 to about 99%.

[0286] In some embodiments, the weight percentage of the organic resin in the nanostructure molded article is about 5 to about 99%, about 5 to about 95%, about 5 to about 90%, about 5 to about 80%, about 5 to about 70%, about 5 to about 60%, about 5 to about 50%, about 5 to about 40%, about 5 to about 30%, about 5 to about 20%, about 5 to about 10%, about 10 to about 99%, about 10 to about 95%, about 10 to about 90%, About 10 to about 80%, about 10 to about 70%, about 10 to about 60%, about 10 to about 50%, about 10 to about 40%, about 10 to about 30%, about 10 to about 20%, about 20 to about 99%, about 20 to about 95%, about 20 to about 90%, about 20 to about 80%, about 20 to about 70%, about 20 to about 60%, about 20 to about 50%, about 20 to about 40%, about 20 to about 30%, about 30 to about 99%, about 30 to about 95%, approximately 30 to approximately 90%, approximately 30 to approximately 80%, approximately 30 to approximately 70%, approximately 30 to approximately 60%, approximately 30 to approximately 50%, approximately 30 to approximately 40%, approximately 40 to approximately 99%, approximately 40 to approximately 95%, approximately 40 to approximately 90%, approximately 40 to approximately 80%, approximately 40 to approximately 70%, approximately 40 to approximately 60%, approximately 40 to approximately 50%, approximately 50 to approximately 99%, approximately 50 to approximately 95%, approximately 50 to approximately 90%, approximately 50 to approximately 80%, about 50 to about 70%, about 50 to about 60%, about 60 to about 99%, about 60 to about 95%, about 60 to about 90%, about 60 to about 80%, about 60 to about 70%, about 70 to about 99%, about 70 to about 95%, about 70 to about 90%, about 70 to about 80%, about 80 to about 99%, about 80 to about 95%, about 80 to about 90%, about 90 to about 99%, about 90 to about 95%, or about 95 to about 99%.

[0287] lighting devices In some embodiments, the nanostructure composition is used to form a light-emitting layer in a lighting device. The lighting device can be used in a wide variety of applications, such as flexible electronics, touchscreens, monitors, televisions, mobile phones, and any other high-resolution display. In some embodiments, the lighting device is a light-emitting diode. In some embodiments, the lighting device is a quantum dot light-emitting diode (QLED). Examples of QLEDs are described in U.S. Patent Application Publication No. 2018 / 0158984, the entire specification of which is incorporated herein by reference.

[0288] In some embodiments, the present disclosure provides: (a) first conductive layer; (b) a second conductive layer; and (c) a light-emitting layer between the first conductive layer and the second conductive layer; a light emitting diode, wherein the light emitting layer comprises at least one population of nanostructures comprising donor-acceptor ligands bound to the nanostructures.

[0289] In some embodiments, the donor-acceptor ligand is a bipolar ligand. In some embodiments, the donor-acceptor ligand is a TADF ligand.

[0290] In some embodiments, the light emitting diode comprises a first conductive layer, a second conductive layer, and a light emitting layer, the light emitting layer being disposed between the first conductive layer and the second conductive layer. In some embodiments, the light emitting layer is a thin film.

[0291] In some embodiments, the light-emitting diode includes additional layers between the first conductive layer and the second conductive layer, such as a hole injection layer, a hole transport layer, and an electron transport layer. In some embodiments, the hole injection layer, the hole transport layer, and the electron transport layer are thin films. In some embodiments, the layers are deposited on a substrate.

[0292]

[0275] When a voltage is applied to the first conductive layer and the second conductive layer, holes injected into the first conductive layer move to the light-emitting layer via the hole injection layer and / or hole transport layer, and electrons injected from the second conductive layer move to the light-emitting layer via the electron transport layer. The holes and electrons recombine in the light-emitting layer to generate excitons.

[0293] Base material

[0276] The substrate can be any substrate commonly used in the manufacture of light-emitting diodes. In some embodiments, the substrate is a transparent substrate such as glass. In some embodiments, the substrate is a flexible material such as polyimide, or a flexible and transparent material such as polyethylene terephthalate. In some embodiments, the substrate has a thickness of about 0.1 to 2 mm. In some embodiments, the substrate is a glass substrate, a plastic substrate, a metal substrate, or a silicone substrate.

[0294] First conductive layer In some embodiments, the first conductive layer is disposed on a substrate. In some embodiments, the first conductive layer is a stack of conductive layers. In some embodiments, the first conductive layer has a thickness of about 50 to about 250 nm. In some embodiments, the first conductive layer is deposited as a thin film using known deposition techniques, such as sputtering or electron beam evaporation. In some embodiments, the first conductive layer comprises indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO), zinc oxide (ZnO), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), silver (Ag), gold (Au), or a mixture thereof. In some embodiments, the first conductive layer is an anode.

[0295] Second conductive layer In some embodiments, the entire layer structure can be sandwiched between a first conductive layer and a second conductive layer. In some embodiments, the first conductive layer acts as the anode of the device, and the second conductive layer acts as the cathode of the device. In some embodiments, the second conductive layer is a metal, such as aluminum. In some embodiments, the second conductive layer has a thickness of about 100 to about 150 nm. In some embodiments, the second conductive layer corresponds to a stack of conductive layers. For example, the second conductive layer can include a layer of silver sandwiched between two layers of ITO (ITO / Ag / ITO).

[0296]

[0279] In some embodiments, the second conductive layer comprises indium tin oxide (ITO), an alloy of indium oxide and zinc oxide (IZO), titanium dioxide, tin oxide, zinc sulfide, silver (Ag), or a mixture thereof.

[0297] Semiconducting polymer layer In some embodiments, the light-emitting diode further includes a semiconducting polymer layer. In some embodiments, the semiconducting polymer layer acts as a hole injection layer. In some embodiments, the semiconducting polymer layer is deposited on the first conductive layer. In some embodiments, the semiconducting polymer layer is deposited by vacuum deposition, spin coating, printing, casting, slot-die coating, or Langmuir-Blodgett (LB) deposition. In some embodiments, the semiconducting polymer layer has a thickness of about 20 to about 60 nm.

[0298] In some embodiments, the semiconducting polymer layer comprises copper phthalocyanine, 4,4',4''-tris[(3-methylphenyl)phenylamino]triphenylamine (m-MTDATA), 4,4',4''-tris(diphenylamino)triphenylamine (TDATA), 4,4',4''-tris[2-naphthyl(phenyl)amino]triphenylamine (2T-NATA), polyaniline / dodecylbenzenesulfonic acid, poly(3,4-ethylenedioxythiophene) / polystyrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid, or polyaniline / poly(4-styrenesulfonate).

[0299] 1st transport layer In some embodiments, the light emitting diode further comprises a transport layer that facilitates transport of electrons and holes affected by an electric field generated between the first conductive layer and the second conductive layer. In some embodiments, the light emitting diode further comprises a first transport layer associated with the first conductive layer. In some embodiments, the first transport layer acts as a hole transport layer (and electron and / or exciton blocking layer). In some embodiments, the first transport layer is deposited on the first conductive layer. In some embodiments, the first transport layer is deposited on the semiconducting polymer layer. In some embodiments, the first transport layer has a thickness of about 20 to about 50 nm. In some embodiments, the first transport layer is substantially transparent to visible light.

[0300] In some embodiments, the first transport layer comprises a material selected from the group consisting of an amine, a triarylamine, a thiophene, a carbazole, a phthalocyanine, a porphyrin, or a mixture thereof. In some embodiments, the first transport layer comprises N,N'-di(naphthalen-1-yl)-N,N'-bis(4-vinylphenyl)-4,4'-diamine, poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl))diphenylamine)], or poly(9-vinylcarbazole).

[0301] 2nd transport layer In some embodiments, the light-emitting diode further comprises a second transport layer. In some embodiments, the second transport layer acts as an electron transport layer (and hole and / or exciton blocking layer). In some embodiments, the second transport layer is in contact with the light-emitting layer. In some embodiments, the second transport layer is disposed between the light-emitting layer and the second conductive layer. In some embodiments, the second transport layer has a thickness of about 20 to about 50 nm. In some embodiments, the second transport layer is substantially transparent to visible light.

[0302] In some embodiments, the second transport layer comprises a material selected from the group consisting of imidazole, pyridine, pyrimidine, pyridazine, pyraxine, oxadiazole, quinoline, chinoxaline, anthracene, benzanthracene, pyrene, perylene, benzimidazole, triazine, ketone, phosphine oxide, phenazine, phenanthroline, triarylborane, metal oxide, and combinations thereof. In some embodiments, the second transport layer is selected from the group consisting of 1,3-bis(3,5-dipyrid-3-ylphenyl)benzene (B3PyPB), bathocuproine, bathophenanthroline, 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole, 2-(4-biphenylyl)-5-phenyl-1,3,4-oxadiazole, 3,5-bis(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole, bis(8-hydroxy-2-methylquinoline)-(4 1-phenylphenoxy)aluminum, 2,5-bis(1-naphthyl)-1,3,4-oxadiazole, 3,5-diphenyl-4-(1-naphthyl)-1H-1,2,4-triazole, 1,3,5-tri(m-pyridin-3-ylphenyl)benzene (TmPyPB), 2,2',2"-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi), tris-(8-hydroxyquinoline)aluminum, TiO, ZnO, SnO, SiO, ZrO, or ZnMgO. In some embodiments, the second transport layer comprises ZnMgO.

[0303]

[0286] When the polarities of the first conductive layer and the second conductive layer are reversed, the roles of the first transport layer and the second transport layer are reversed.

[0304] Light-emitting layer Sandwiched between the first and second transport layers is an emissive layer comprising at least one population of nanostructures comprising donor-acceptor ligands bound to the nanostructures. The emissive layer can be formed by depositing a mixture of at least one population of nanostructures comprising donor-acceptor ligands bound to the nanostructures with a solvent and evaporating the solvent. In some embodiments, the solvent evaporates at room temperature. In some embodiments, heat is applied to the deposited film to facilitate evaporation of the solvent. In some embodiments, the nanostructure-solvent mixture is deposited using a spin-coating technique. In some embodiments, the emissive layer has a thickness of about 10 to about 50 nm. [Example]

[0305] Example

[0288] The following examples are illustrative, but not limiting, of the products and methods described herein. Suitable modifications and adaptations of the variety of conditions, formulations, and other parameters normally encountered in this field and obvious to those skilled in the art in light of this disclosure are within the spirit and scope of the present invention.

[0306] Example 1 [ka] Synthesis of 2,6-di(9H-carbazol-9-yl)isonicotinic acid To a solution of potassium tert-butoxide (0.672 g, 6 mmol) in anhydrous N,N-dimethylformamide (20 mL), 9H-carbazole (1.002 g, 6 mmol) in anhydrous N,N-dimethylformamide (20 mL) was added dropwise over 15 minutes, followed by stirring for 3 hours. A solution of tert-butyl 2,6-dichloroisonicotinate (0.7443 g, 3 mmol) in anhydrous N,N-dimethylformamide (10 mL) was added dropwise over 15 minutes. The solution was then stirred at 80° C. for 10 hours. Sodium bicarbonate (350 g) dissolved in water was then added to the solution, and the white precipitate was filtered and dried under vacuum. The product was purified by column chromatography on silica gel.

[0307]

[0290] While various embodiments have been described above, it should be understood that they have been presented by way of example only, and not limitation. It will be apparent to those skilled in the relevant art that various changes in form and detail can be made therein without departing from the spirit and scope of the present invention. Accordingly, its breadth and scope should not be limited by any of the exemplary embodiments described above, but should be defined only in accordance with the following claims and equivalents thereof.

[0308]

[0291] Any patents and patent applications mentioned in this specification are indicative of the level of skill of those skilled in the art to which this invention pertains, and are hereby incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually incorporated by reference herein.

Claims

1. (a) at least one quantum dot; and (b) at least one donor-acceptor ligand; wherein the donor-acceptor ligand comprises at least one terminal functional group, and the at least one terminal functional group is attached to a surface of the quantum dot; The donor-acceptor ligand is of Formula I or Formula II: D ｄ -A ａ -FG ｆ (I) or A ａ -D ｄ -FG ｆ (II) and at least one selected from the group consisting of radicals of compounds having a structure represented by In the above formula I or II, FG is —CO ２ H; D is a carbazole-containing donor moiety optionally substituted with one or more substituents; A is an acceptor moiety comprising any one or more selected from the group consisting of pyridine, pyrimidine, pyrazine and triazine, optionally substituted with one or more substituents; Quantum dot-containing compositions.

2. The donor-acceptor ligand is one or more selected from the group consisting of radicals of the following compounds: The quantum dot-containing composition of claim 1 . 【Chemical 44】

3. The donor-acceptor ligand is a radical of the following compound: The quantum dot-containing composition according to claim 1 or 2. 【143】

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