ZHANG CHENG (US)
LIU WEI (US)
WANG SIHONG (US)
CLAIMS What is claimed is: 1. A stretchable light-emitting polymer of formula (I), (II), (III), (IV), or (V): wherein D is a donor chemical moiety capable of donating electrons; A is an acceptor chemical moiety capable of accepting electrons; T is a chemical moiety comprising D bonded to A; S is a stretchable section, comprising a stretchable chemical moiety selected from the group consisting m is an integer from 1 to 100; n is an integer from 1 to 50; and a dihedral angle of a bond between D and A is from about 75.0° to about 90.0°. 2. The polymer of claim 1, wherein the stretchable section comprises a stretchable chemical moiety selected from the group consisting of ; wherein R is a linker moiety, bonded in either direction, selected from the group consisting 3. The polymer of claims 1 - 2, wherein the donor chemical moiety is selected from the group consisting of: and wherein the donor chemical moiety is bonded to the acceptor chemical moiety at a carbon or nitrogen atom of the donor chemical moiety. 4. The polymer of claims 1 – 3, wherein the acceptor chemical moiety is selected from the group consisting of: wherein the acceptor chemical moiety is bonded to the donor chemical moiety at a carbon, nitrogen, boron, or sulfur atom, and the acceptor chemical moiety is bonded to each of two stretchable sections at each of a second and a third carbon, nitrogen, boron, or sulfur atom. 5. The polymer of claims 1 – 4, wherein the polymer is selected from the group consisting of: 6. The polymer of claims 1 – 5, wherein the polymer exhibits a charge transfer absorption at a wavelength of from 350 to 400 nanometers, and a second charge transfer absorption at a wavelength of from 400 to 450 nanometers 7. The polymer of claims 1 – 6, wherein the polymer exhibits a prompt decay of about 10 nanoseconds and a delayed decay of about 3 microseconds. 8. The polymer of claims 1 – 7, wherein the polymer exhibits a crack on-set strain of greater than 100%. 9. A stretchable organic light-emitting diode, comprising: a cathode layer; an anode layer; a film comprising a stretchable light-emitting polymer of formula (I), (II), (III), (IV), or (V): a stretchable electron injection layer between the cathode layer and the film; and a stretchable hole transporting layer between the anode layer and the film; wherein D is a donor chemical moiety capable of donating electrons; A is an acceptor chemical moiety capable of accepting electrons; T is a chemical moiety comprising D bonded to A; S is a stretchable section, comprising a stretchable chemical moiety selected from the group consisting m is an integer from 1 to 100; n is an integer from 1 to 50; and a dihedral angle of a bond between D and A is from about 75.0° to about 90.0°. 10. The diode of claim 9, wherein the stretchable section comprises a stretchable chemical moiety selected from the group consisting of ; wherein R is a linker moiety, bonded in either direction, selected from the group consisting 11. The diode of claims 9 – 10, wherein the donor chemical moiety is selected from the group consisting of: and wherein the donor chemical moiety is bonded to an acceptor chemical moiety at a carbon or nitrogen atom of the donor chemical moiety. 12. The diode of claims 9 – 11, wherein the acceptor chemical moiety is selected from the group consisting of: wherein the acceptor chemical moiety is bonded the donor chemical moiety at a carbon, nitrogen, boron, or sulfur atom, and the acceptor chemical moiety is bonded to each of two stretchable sections at each of a second and a third carbon, nitrogen, boron, or sulfur atom. 13. The diode of claims 9 - 12, wherein the polymer is selected from the group 14. The diode of claims 9 – 13, wherein the cathode layer and the anode layer comprise thermoplastic polyurethane comprising transparent silver nanowire. 15. The diode of claims 9 – 14, wherein the electron injection layer comprises poly[(9,9-bis(3’-((N,N-dimethyl)-N-ethylammonium)-propyl)-2,7-fluorene)-alt-2,7-(9,9- dioctylfluorene)] (PFN-Br) and polyethyleneimine ethoxylated (PEIE) in a weight ratio of from about 2:1 to about 1:4. 16. The diode of claims 9 – 15, wherein the hole transporting layer comprises poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) with perfluorinated ionomers (PFI) in a weight ratio of from about 3:1 to about 1:50. 17. The diode of claims 9 – 16, wherein the diode is configured to exhibit a maximum external quantum efficiency of about 10% during stretching to 100% strain. 18. The diode of claims 9 – 17, wherein the diode is configured to exhibit a maximum external quantum efficiency of about 3.3% during stretching to 60% strain. 19. A stretchable light-emitting polymer of formula (VI): wherein m is an integer from 1 to 100; and n is an integer from 1 to 50. 20. The polymer of claim 19, wherein the polymer exhibits a charge transfer absorption at a wavelength of from 350 to 400 nanometers, and a second charge transfer absorption at a wavelength of from 400 to 450 nanometers. 21. The polymer of claims 19 – 20, wherein the polymer exhibits a prompt decay of about 10 nanoseconds and a delayed decay of about 3 microseconds. 22. The polymer of claims 19 – 21, wherein the polymer exhibits a crack on-set strain of greater than 100%. |
[0136] In a double-necked 150-milliliter round-bottom flask with a magnetic stir bar, reflux condenser, and N 2 atmosphere, toluene (20 mL) was added to a mixture of (4-bromophenyl)(4- fluorophenyl)methanone (1.1 g, 4 mmol), 9,9-dimethyl-9,10-dihydroacridine (0.81 g, 4 mmol), bis(dibenzylideneacetone)dipalladium (“Pd(dba)2”) (0.115 g, 0.2 mmol), NaOtBu (0.96 g, 10.0 mmol), and dicyclohexylphosphino-2’,4’,6-tri-i-propyl-1,1’-biphen yl (“Xphos”) (0.28 g, 0.6 mmol). The mixture was refluxed for 12 hours under a N 2 atmosphere. After the mixture was cooled to room temperature, the reaction mixture was extracted using dichloromethane and distilled water. The dichloromethane (“DCM”) phase was dried over Na2SO4 and then filtered. After the solvent was removed under reduced pressure, the residue was purified by column chromatography on silica gel using hexane/DCM (v/v = 4:1) as eluent to give the product, after removal of solvent under reduced pressure, as a yellow powder (Compound 1, 1.28 g, yield 81%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.07 – 8.01 (m, 2H), 8.00 – 7.92 (m, 2H), 7.54 – 7.44 (m, 4H), 7.25 – 7.19 (m, 2H), 7.05 – 6.92 (m, 4H), 6.33 (dd, J = 8.0, 1.4 Hz, 2H), 1.70 (s, 6H). The 1 H NMR spectrum of Compound 1 is illustrated in FIG.1. [0137] 2. Preparation of (4-(2,7-dibromo-9H-carbazol-9-yl)phenyl)(4-(9,9-dimethylacri din- 10 -yl)phenyl)methanone (Compound 2):
[0138] A mixture of Compound 1 (1.22 g, 3 mmol) and 2,7-dibromo-9H-carbazole (1.03 g, 3.2 mmol) in N,N-dimethylformamide (15 mL) was stirred for 15 minutes under argon atmosphere at room temperature, and then the reaction mixture was heated up to 110°C and potassium tert- butoxide (0.35 g, 3.1 mmol) was added, followed by stirring for 12 hours. The reaction was quenched with water (20 mL), and precipitated in methanol, filtered by vacuum, and washed with methanol three times to obtain the crude product as a yellow powder (Compound 2, 2.01 g, yield 90%). 1 H NMR (400 MHz, CDCl3) δ 8.19 (dd, J = 12.4, 8.3 Hz, 4H), 7.97 (d, J = 8.3 Hz, 2H), 7.73 (d, J = 8.3 Hz, 2H), 7.63 (d, J = 1.6 Hz, 2H), 7.56 (d, J = 8.2 Hz, 2H), 7.50 (dd, J = 7.7, 1.6 Hz, 2H), 7.45 (dd, J = 8.3, 1.6 Hz, 2H), 7.02 (tdd, J = 14.9, 10.5, 4.6 Hz, 4H), 6.39 (d, J = 8.0 Hz, 2H), 1.71 (s, 6H). The 1 H NMR spectrum of Compound 2 is illustrated in FIG. 2. [0139] 3. Preparation of (4-(2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H- carbazol-9-yl)phenyl)(4(9,9-dimethylacridin-10(9H)-yl)phenyl )methanone (Compound 3):
[0140] Compound 2 (1.42 g, 2 mmol), bis(pinacolato)diboron (1.52 g, 6 mmol), [1,1’- Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (73 mg, 0.1 mmol), and potassium acetate (0.59 g, 6 mmol) were mixed in a flask that was vacuumed and filled with a nitrogen atmosphere three times. Degassed DMF (15 mL) was added and the system was heated to 100°C and stirred for 12 hours. When the temperature cooled down to room temperature, the mixture was precipitated into 100 mL saturated sodium chloride solution, filtered by vacuum to obtain the crude product, and purified by column chromatography on silica gel (short ~ 15 cm) using first Hexane/DCM in a 1:3 v/v ratio, and then DCM, as eluent, to give the product, after removal of solvent under reduced pressure, as a yellow powder (Compound 3, 0.81 g, yield 50.1%). 1 H NMR (400 MHz, CDCl3) δ 8.29 – 8.13 (m, 6H), 7.95 (s, 2H), 7.80 (t, J = 7.8 Hz, 4H), 7.56 (d, J = 8.4 Hz, 2H), 7.49 (d, J = 7.7 Hz, 2H), 7.01 (dt, J = 13.7, 7.3 Hz, 4H), 6.38 (d, J = 7.0 Hz, 2H), 1.72 (s, 6H), 1.36 (s, 24H). The 1 H NMR spectrum of Compound 3 is illustrated in FIG.3. [0141] The Trz-tBuCz monomer was synthesized according to the following Scheme A1: [0142] 4. Preparation of 2,4-bis(4-bromo-3-methylphenyl)-6-(4-fluoro-3-methylphenyl)- 1,3,5-triazine (Compound 9): [0143] 4-fluoro-3-methylbenzoyl chloride (1.72 g, 10 mmol) and 4-bromo-3- methylbenzonitrile (3.92 g, 20 mmol) were added to chlorobenzene (30 mL) and the solution was cooled to 0 °C. To the solution, antimony(V) chloride (3.00 g, 10 mmol) was added drop- wise. The mixture was stirred for 20 minutes and warmed to room temperature, then heated at 100 °C for 2 hours. The resulting orange slurry of the oxadiazinium salt was cooled to 0 °C. With vigorous stirring, 28% NH 3 aqueous solution (40 mL) was added to the slurry, and a white precipitate of Compound 9 was immediately formed as a white slurry. The precipitate was collected by filtration and washed with a mixture of water and methanol. The product was purified by column chromatography on silica gel using hexane/dichloromethane (“DCM”) (v/v = 4:1) as eluent to give a white solid product after removal of solvent under reduced pressure (Compound 9, 2.9 g, yield 55.0 %). 1 H NMR (400 MHz, CDCl3) δ 8.65 – 8.45 (m, 4H), 8.39 (dd, J = 8.3, 2.1 Hz, 2H), 7.72 (d, J = 8.3 Hz, 2H), 7.23 – 7.13 (m, 1H), 2.57 (s, 6H), 2.43 (t, J = 6.5 Hz, 3H). The 1 H NMR spectrum of Compound 9 is illustrated in FIG.67. [0144] 5. Preparation of 9-(4-(4,6-bis(4-bromo-3-methylphenyl)-1,3,5-triazin-2-yl)-2- methylphenyl)-3,6-di-tert-butyl-9H-carbazole (Compound 10):
[0145] A solution of Compound 9 (0.58 g, 1 mmol), 3,6-di-tert-butylcarbazole (0.28 g, 1 mmol), and cesium carbonate (1.63 g, 5 mmol) in N,N-dimethylformamide (DMF) was stirred for 30 minutes under nitrogen atmosphere, and then stirred for 12 hours at 105 °C. After the mixture was cooled to room temperature, the reaction mixture was extracted using dichloromethane and distilled water. The DCM phase was dried over sodium sulfate and filtered. After the solvent was removed under reduced pressure, purification was carried out with column chromatography on silica gel using hexane/DCM (v/v = 5:1) as eluent to give the product as a white powder (Compound 10, 0.65 g, yield 83.1%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.81 (s, 1H), 8.72 (dd, J = 8.1, 1.8 Hz, 1H), 8.63 (d, J = 1.7 Hz, 2H), 8.46 (dd, J = 8.4, 2.0 Hz, 2H), 8.18 (d. J = 1.7 Hz, 2H), 7.76 (d, J = 8.4 Hz, 2H), 7.57 (d, J = 8.2 Hz, 1H), 7.46 (dd, J = 8.6, 1.9 Hz, 2H), 7.03 (d, J = 8.6 Hz, 2H), 2.60 (s, 6H), 2.22 (s, 3H), 1.48 (s, 18H). The 1 H NMR spectrum of Compound 10 is illustrated in FIG.68. [0146] 6. Preparation of 2-(4-(diphenylamino)phenyl)anthracene-9,10-dione (“TPA-AQ,” Compound 13): [0147] 2-bromoanthraquinone (0.33 g, 1.2 mmol), [4-(diphenylamino)phenyl]boronic acid (0.69 g, 2.4 mmol), Pd(PPh 3 ) 4 (50 mg), and K 2 CO 3 (2.2 g, 16 mmol) in THF (20 mL) and deionized water (8 mL) were stirred under nitrogen at 65 °C for 12 h. After the mixture was cooled to room temperature, the reaction mixture was extracted using dichloromethane and distilled water. The DCM phase was dried over sodium sulfate and filtered. After the solvent was removed under reduced pressure, purification was carried out with column chromatography on silica gel using hexane/DCM (v/v = 4:1) as eluent to give the product as a white powder (Compound 13, 0.48 g, yield 89.3%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.51 (d, J = 1.9 Hz, 1H), 8.38 – 8.30 (m, 3H), 7.99 (dd, J = 8.2, 2.0 Hz, 1H), 7.85 – 7.76 (m, 2H), 7.65 – 7.59 (m, 2H), 7.35 – 7.27 (m, 4H), 7.20 – 7.14 (m, 6H), 7.12 – 7.04 (m, 2H). The 1 H NMR spectrum of Compound 13 is illustrated in FIG.71. [0148] B. General Procedure B: Synthetic preparation of alkyl chain monomers. [0149] The alkyl chain monomers (Compounds 4 – 7) were synthesized according to the following Scheme B: [0150] A solution of 4-bromo-3-methylphenol (15 mmol), diiodoalkane (6 mmol), and tetrabutylammonium bromide (TBAB, 4 mg, 0.15 mmol) in 12 mL THF was stirred for 30 minutes under nitrogen at 65°C, and then sodium hydroxide (NaOH, 0.6 g, 15 mmol) in 3 mL THF was added and stirred for 12 hours. After cooling to room temperature, the solution was poured into methanol. The precipitate was collected by filtration and washed with water/methanol. Finally, the precipitate was purified by column chromatography on silica gel using hexane:DCM in a 4:1 v/v ratio as eluent to give a white solid product. [0151] 1. Preparation of bis(4-bromo-3-methylphenoxy)methane (Compound 4): [0152] Synthesized by general procedure B to give the product as a white solid (Compound 4, 0.90 g, yield 39.0%). 1 H NMR (400 MHz, CDCl3) δ 7.42 (d, J = 8.7 Hz, 2H), 6.97 (d, J = 2.7 Hz, 2H), 6.81 (dd, J = 8.7, 2.8 Hz, 2H), 5.64 (s, 2H), 2.37 (s, 6H). The 1 H NMR spectrum of Compound 4 is illustrated in FIG.4. [0153] 2. Preparation of 1,3-bis(4-bromo-3-methylphenoxy)propane (Compound 5): [0154] Synthesized by general procedure B to give the product as a white solid (Compound 5, 0.7 g, yield 28.3%). 1 H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 8.7 Hz, 2H), 6.79 (d, J = 3.0 Hz, 2H), 6.61 (dd, J = 8.7, 3.0 Hz, 2H), 4.10 (t, J = 6.1 Hz, 4H), 2.35 (s, 6H), 2.29 – 2.14 (m, 2H). The 1 H NMR spectrum of Compound 5 is illustrated in FIG.5. [0155] 3. Preparation of 1,6-bis(4-bromo-3-methylphenoxy)hexane (Compound 6): [0156] Synthesized by general procedure B to give the product as a white solid (Compound 6, 1.9 g, yield 69.8%). 1 H NMR (400 MHz, CDCl3) δ 7.38 (dd, J = 8.7, 1.9 Hz, 2H), 6.78 (s, 2H), 6.60 (dd, J = 8.7, 2.3 Hz, 2H), 3.92 (td, J = 6.4, 1.9 Hz, 4H), 2.35 (d, J = 1.5 Hz, 6H), 1.82 (dd, J = 32.3, 3.9 Hz, 4H), 1.52 (d, J = 1.9 Hz, 4H). The 1 H NMR spectrum of Compound 6 is illustrated in FIG.6. [0157] 4. Preparation of 1,10-bis(4-bromo-3-methylphenoxy)decane (Compound 7): [0158] Synthesized by general procedure B to give the product as a white solid (Compound 7, 1.0 g, yield 32.7%). 1 H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 8.7 Hz, 2H), 6.78 (d, J = 2.9 Hz, 2H), 6.60 (dd, J = 8.7, 3.0 Hz, 2H), 3.90 (t, J = 6.5 Hz, 4H), 2.35 (s, 6H), 1.84 – 1.67 (m, 4H), 1.43 (dd, J = 14.4, 6.9 Hz, 4H), 1.3 (s, 8H). The 1 H NMR spectrum of Compound 7 is illustrated in FIG.7. [0159] 5. Preparation alkyl chain monomer 1,1-bis(4-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)phenoxy)decane (Compound 11): [0160] A solution of 1,10-dibromodecane (0.9 g, 3 mmol), 4-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)phenol (2.64 g, 12 mmol), and potassium carbonate (K 2 CO 3 , 1.65 g, 12 mmol) in 40 mL of acetone were stirred under nitrogen at 60 °C for 40 h. After the mixture was cooled to room temperature, the reaction mixture was extracted using DCM and distilled water. The DCM phase was dried over sodium sulfate and then filtered. After the solvent was removed under reduced pressure, purification was carried out with column chromatography on silica gel using hexane/ethyl acetate (v/v = 10:1) as eluent to give Compound 11 as a white powder (1.15 g, yield 66.3%). 1 H NMR (400 MHz, CDCl3) δ 7.79 – 7.69 (m, 4H), 6.93 – 6.83 (m, 4H), 3.97 (t, J = 6.6 Hz, 4H), 1.84 – 1.72 (m, 4H), 1.51 – 1.40 (m, 4H), 1.33 (s, 32H). The 1 H NMR spectrum of Compound 11 is illustrated in FIG.69. [0161] C. Synthetic Preparation of (4-(2,7-bis(4-methoxy-2-methylphenyl)-9H-carbazol-9- yl)phenyl)(4-(9,9-dimethylacridin-10(9H)-yl)phenyl)methanone (“DKC”) (Compound 8). [0162] DKC (Compound 8) was synthesized according to the following Scheme C:
[0163] 1. (4-(2,7-bis(4-methoxy-2-methylphenyl)-9H-carbazol-9-yl)pheny l)(4-(9,9- dimethylacridin-10 -yl)phenyl)methanone (DKC, Compound 8): [0164] 4-Bromo-3-methylanisole (0.3 g, 1.5 mmol), Compound 3 (0.48 g, 0.6 mmol), tris(dibenzylideneacetone)dipalladium (1.5 mg), and 2-dicyclohexylphosphino-2’,6’- dimethoxybiphenyl (“Sphos”) (7 mg) were charged into a flask that was then vacuumed and aerated with argon five times. Degassed toluene (20 mL) was added, and the mixture was heated to 80°C under vigorous stirring. A potassium carbonate solution (8 mL, 2 mol/L in H 2 O) with four drops of Aliquat 336 was added, and the temperature was raised to 95°C. After the mixture was cooled to room temperature, the reaction mixture was extracted using dichloromethane and distilled water. The dichloromethane phase was dried over Na2SO4 and then was filtered. After the solvent was removed under reduced pressure, the residue was purified by column chromatography on silica gel using hexane/DCM in a 2:1 v/v ratio as eluent to give the product (Compound 8, 0.41 g, yield 87%). 1 H NMR (400 MHz, CDCl3) δ 8.26 – 8.01 (m, 6H), 7.81 (d, J = 8.5 Hz, 2H), 7.61 – 7.39 (m, 6H), 7.35 – 7.19 (m, 4H), 6.99 (ddd, J = 10.3, 7.5, 1.5 Hz, 4H), 6.89 – 6.76 (m, 4H), 6.36 (dd, J = 7.9, 1.4 Hz, 2H), 3.83 (s, 6H), 2.31 9s, 6H), 1.7 (s, 6H). The 1 H NMR spectrum of Compound 8 is illustrated in FIG.8. [0165] C1. Synthetic Preparation of 9-(4-(4,6-bis(4’-methoxy-2-methyl-[1,1’-biphenyl]-4- yl)-1,3,5-triazin-2-yl)-2-methylphenyl)-3,6-di-tert-butyl-9H -carbazole (“Trz-tBuCz”) (Compound 12): [0166] Compound 10 (0.78 g, 1 mmol), 4-methoxyphenylboronic acid pinacol ester (0.84 g, 3.6 mmol), Pd(PPh3)4 (100 mg), and K2CO3 (2.2 g, 16 mmol) in tetrahydrofuran (“THF,” 20 mL) and deionized water (8 mL) were stirred under nitrogen at 65 °C for 12 h. After the mixture was cooled to room temperature, the reaction mixture was extracted using DCM and distilled water. The DCM phase was dried over sodium sulfate and then filtered. After the solvent was removed under reduced pressure, purification was carried out with column chromatography on silica gel using hexane/DCM (v/v = 1:1) as eluent, to give the product as a white powder (Compound 12, 0.65 g, yield 89.2%). 1 H (400 MHz, CDCl 3 ) δ 8.87 (d, J = 1.3 Hz, 1H), 8.79 (dd, J = 8.2, 1.7 Hz, 1H), 8.67 (dd, J = 11.6, 3.6 Hz, 4H), 8.19 (d, J = 1.6 Hz, 2H), 7.57 (d, J = 8.2 Hz, 1H), 7.47 (dd, J = 8.2, 2.6 Hz, 4H), 7.40 – 7.33 (m, 4H), 7.09 – 6.98 (m, 6H), 3.89 (s, 6H), 2.49 (s, 6H), 2.23 (s, 3H), 1.48 (s, 18H). The 1 H spectrum of Compound 12 is illustrated in FIG.70. [0167] D. Preparation of stretchable light-emitting polymer by Suzuki poly-condensation. [0168] Stretchable light-emitting polymers were synthesized according to the following Scheme D: [0169] Compound 3 (0.6 mmol), alkyl chain monomer (0.6 mmol), tris(dibenzylideneacetone)dipalladium (1.5 mg), and 2-dicyclohexylphosphino-2’,6’- dimethoxybipehnyl (Sphos) (7 mg) was charged into a flask, which was then vacuumed and aerated with argon five times. Degassed toluene (20 mL) was added, and the mixture was heated to 80°C under vigorous stirring. A degassed potassium carbonate solution (8 mL, 2 mol/L in H2O) with four drops of Aliquat 336 was added, and the temperature was increased to 95°C. After 5 days of reaction, 4-bromo-3-methylanisole (50 mg in 3 mL toluene) was added. After 8 hours, phenylboronic acid (100 mg in 3 mL toluene) was added. After another 8 hours, the mixture was cooled down to 80°C, then sodium diethyldithiocarbamate trihydrate (10 mL, 1 g/mL in H2O) was added. After 24 hours, the system was cooled down to room temperature. The mixture was poured into 100 mL DCM and washed with 100 mL saturated sodium chloride solution five times. The separated organic layer was dried over sodium sulfate, concentrated by rotary evaporation to 8 mL solution. The mixture was precipitated into 200 mL methanol and filtered by vacuum to obtain the crude fiber product. The product was further purified by bathing in boiling methanol, acetone, and chlorobenzene by Soxhlet’s extractor. Then the chlorobenzene solution product was concentrated by rotary evaporation to 6 ml, precipitated into 200 mL methanol, filtered by vacuum to obtain pure yellow fiber (stretchable light-emitting polymer). [0170] By the above process, the five example stretchable light-emitting polymers illustrated below in Scheme E were synthesized. The first four example polymers include the same TADF units, but differ in the length of the alkylene chain. The alkylene chain lengths include 1 carbon, 3 carbons, 6 carbons, and 10 carbons for each of PDKCM, PDKCP, PDKCH, and PDKCD, respectively. The 1 H spectra for each of PDKCM, PDKCP, PDKCH, and PDKCD are illustrated in FIGs. 9 – 12, respectively. The fifth example stretchable light-emitting polymer, PTrz-tBuCz, is prepared from Compounds 11 and 12, and a 1 H spectrum for PTrz- tBuCz is illustrated in FIG.72.
Scheme E [0171] The number average molecular weights (M n ) and weight average molecular weights (Mw) in kilodaltons (kDa), and polydispersity indices (PDI), of PDKCM, PDKCP, PDKCH, PDKCM, and PTrz-tBuCz are provided below in Table 1. TABLE 1 Molecular weights of stretchable light-emitting polymers. [0172] E. Analysis of EL Efficiency. [0173] Without wishing to be bound by theory, it is believed that in the four example polymers, the acridine-benzophenone moiety, which is characterized by a close-to-perpendicular dihedral angle, serves as the electron donor-acceptor (“D-A”) pair and provides high EL efficiency. Taking example polymer PDKCD as a particular example, as illustrated in FIG. 13, the optimized conformational structure of PDKCD, as estimated by density functional theory (“DFT”), demonstrates that the dihedral angle of the D-A pair is close to 90 degrees. Based on the approximately perpendicular dihedral angle of the D-A pair of PDKCD, it is expected that PDKCD will have a small energy-level splitting between singlet (S1) and triplet (T1) excited states, and provide high EL efficiency. [0174] FIG. 14 illustrates optical microscope images of films of each of the four example stretchable light-emitting polymers shown in Scheme E, horizontally stretched, at approximately the on-set strains for crack formation. FIG. 15 illustrates the glass-transition temperatures of each of the four example stretchable light-emitting polymers shown in Scheme E, obtained from DSC thermal analysis of the four stretchable light-emitting polymers. FIG. 16 illustrates the trends in crack on-set strains and glass-transition temperatures of the four stretchable light-emitting polymers. The crack on-set strains and glass-transition temperatures illustrated in FIGs.14 and 15, respectively, and the trends illustrated in FIG.16, confirm that a longer alkylene chain of 10 carbons may more effectively enhance chain dynamics and may increase stretchability of the stretchable light-emitting polymer to greater than 125% strain. [0175] As illustrated in FIG. 17, the example stretchable light-emitting polymers, PDKCM, PDKCP, PDKCH, and/or PDKCD, may serve as an emitting layer, thereby combining high EL efficiency and brightness and high stretchability in novel, fully stretchable EL devices. [0176] F. Analysis of Effect of Alkylene Chain Length on Photophysical Properties of Exemplary Stretchable Light-Emitting Polymers. [0177] The influence of the alkylene chain length was analyzed by combining comprehensive experimental characterizations and theoretical simulations with DFT and molecular dynamics (“MD”). For comparison, small-molecule emitter DKC (Compound 8) was also synthesized. As illustrated in FIG.18, each of PDKCM, PDKCP, PDKCH, PDKCD, and DKC exhibits two charge transfer (“CT”) absorptions: CT 2 at a wavelength of 350-400 nanometers, and CT 1 at a wavelength of 400-450 nanometers. Without being bound by theory, it is believed that CT2 absorption corresponds to a carbazole-to-benzophenone charge transfer, and CT1 absorption corresponds to an acridine-to-benzophenone transfer. Because one emission peak corresponding to CT1 is exhibited by each of PDKCM, PDKCP, PDKCH, PDKCD, and DKC as illustrated by FIG. 18, minimal difference is observed in the PL emission spectra among PDKCM, PDKCP, PDKCH, PDKCD, and DKC. [0178] Low-temperature FL/PH spectroscopy was performed to study the energy-level splitting (ΔEST) of each of PDKCM, PDKCP, PDKCH, PDKCD, and DKC. FL/PH spectra of solutions of each of PDKCM, PDKCP, PDKCH, PDKCD, and DKC in 2- methyltetrahydrofuran (“2-Me-THF,” 10 -5 M) at low temperature (77 K) are illustrated in FIG. 19A. FL/PH spectra of films of each of PDKCM, PDKCP, PDKCH, PDKCD, and DKC at low temperature are illustrated in FIG. 19B. In solution in 2-Me-THF, the ΔEST, which corresponds to the CT 2 emission, demonstrated a trend of gradually decreasing with increase of alkylene chain length for polymers PDKCM, PDKCP, PDKCH, and PDKCD. Without being bound by theory, it is believed that the gradual slight decrease in ΔEST with increasing alkylene chain length demonstrated in FIG. 19A as observed in 2-Me-THF solution may be due to the disappearance of conjugation coupling between adjacent carbazole moieties. By contrast, for each of PDKCM, PDKCP, PDKCH, PDKCD, and DKC in the film state, with complete energy transfer from CT 2 to CT 1 as illustrated in FIG.19B, the ΔE ST values are nearly identical, and the values are such as to provide efficient thermally activated delayed fluorescence. The D-A pair dihedral angle distributions for the four polymers PDKCM, PDKCP, PDKCH, and PDKCD in MD simulation, as illustrated in FIG.20, further support the conclusions drawn from the ΔE ST values. [0179] The PL quantum yield (“PLQY”) and transient PL decay were tested to further quantify the TADF of the four polymers PDKCM, PDKCP, PDKCH, and PDKCD. From the transient PL decay measurements, the four polymers PDKCM, PDKCP, PDKCH, and PDKCD, and DKC all demonstrate both prompt decay of approximately 10 nanoseconds, as illustrated in FIGs.21A – 21E, and delayed decay of approximately 3 microseconds, as illustrated in FIGs. 22A – 22E. The prompt decay of approximately 10 nanoseconds and delayed decay of approximately 3 microseconds provide direct evidence for thermally activated delayed fluorescence. The PL quantum yields for the four polymers PDKCM, PDKCP, PDKCH, and PDKCD are similar to the PL quantum yield for DKC, as illustrated in FIG.23. [0180] The kinetic rate parameters for PDKCM, PDKCP, PDKCH, PDKCD, and DKC were estimated, and the parameters are summarized in Table 2 below. As the data in Table 2 demonstrates, the parameters for the polymers and DKC are highly similar, indicating that the alkylene chain length of the four polymers does not detract from the rates of the individual steps in the TADF process. In Table 2, τp and τd correspond, respectively, to the prompt and delayed decay times estimated from the transient PL decay data; k p and k d correspond, respectively, to the prompt and delayed fluorescence decay rate constants; Φ F and Φ TADF correspond, respectively, to the prompt and delayed fluorescence quantum efficiencies; kr S corresponds to the radiative decay rate constant at singlet S 1 state; k ISC and k RISC correspond, respectively, to the rate constants for the intersystem crossing (“ISC”) process from singlet S 1 to triplet T1 states, and the reverse ISC (“RISC”) process from triplet T1 to singlet S1 states; and knr T corresponds to the non-radiative decay rate constant at triplet state. TABLE 2 Kinetic rate parameters of DKC and exemplary stretchable light-emitting polymers a Calculated using single-exponential decay fitting for the prompt component in the range of 50 ns; b Calculated using double-exponential decay fitting for the delayed component in the range of 5 µs. [0181] G. Analysis of EL Properties of Exemplary Stretchable Light-Emitting Polymers as Host-Free Emitting Layers in Conventional OLED Structure. [0182] The EL properties of PDKCM, PDKCP, PDKCH, PDKCD, and DKC were separately included as the emitting layer in an OLED structure, a schematic of an example of which is illustrated in FIG.24. As illustrated in FIG.25, the four exemplary stretchable light-emitting polymers PDKCM, PDKCP, PDKCH, and PDKCD demonstrate very similar current density- voltage and luminance-voltage traces. Compared with an example of an OLED including DKC, the maximum luminance of examples of OLEDs including one of the four exemplary stretchable light-emitting polymers is slightly decreased. Without being bound by theory, it is believed that the slight decrease in maximum luminance of examples of OLEDS including an exemplary stretchable light-emitting polymer may be a result of the different packing structures of TADF units in polymer chains relative to the packing structure of small-molecule DKC. As illustrated in FIG.26, the luminescence spectra of OLEDs including an exemplary stretchable light-emitting polymer and an OLED including DKC are also highly similar. [0183] Similar EL performance between an OLED including DKC and OLEDs including an exemplary stretchable light-emitting polymer is also demonstrated by external quantum efficiency (EQE), which is illustrated by FIG. 26. As illustrated in FIG. 26, exemplary stretchable light-emitting polymers PDKCM, PDKCP, PDKCH, and PDKCD achieve a maximum EQE of approximately 10%. The maximum EQE values of OLEDs including an exemplary stretchable light-emitting polymer is similar to maximum EQE values for OLEDs including one of the reported non-stretchable TADF polymers as a host-free emitter, as demonstrated by Table 3. TABLE 3 Molecular Weights and Maximum EQE Values of Reported TADF Polymers and Exemplary Stretchable Light-Emitting Polymers in OLEDs a Data unavailable, but molecular weight is likely relatively low because the polymer was purified with a regular silica gel column. b Hole transporting layer is PEDOT:PSS. c Hole transporting layer is PEDOT:PSS_PFI composite. TSCT = Through-space charge transfer. [0184] As used in Table 3, the term “LEP” refers to the TADF polymer represented by the following chemical structure: . [0185] As used in Table 3, the term “poly(AcBPCz-TMP)” refers to the TADF polymer represented by the following chemical structure: . [0186] As used in Table 3, the term “poly(TMTPA-DCB)” refers to the TADF polymer represented by the following chemical structure: . [0187] As used in Table 3, the term “P12,” where x = 0.12, refers to the TADF polymer represented by the following chemical structure: . [0188] As used in Table 3, the term “PABPC5,” where x = 5, refers to the TADF polymer represented by the following chemical structure: . [0189] As used herein, the term “PCzATD5,” where x = 5, refers to the TADF polymer represented by the following chemical structure: . [0190] As used in Table 3, the terms “PAPTC,” where x = 50, and “PCzAPT10,” where x = 10 refer to the TADF polymers represented by the following chemical structure: . [0191] As used in Table 3, the term “PBD-10,” where x = 0.10, refers to the TADF polymer represented by the following chemical structure: . [0192] As used in Table 3, the term “PAPCC” refers to the TADF polymer represented by the following chemical structure: . [0193] As used in Table 3, the term “P-Ac95-TRZ05,” where x = 0.05, refers to the TADF polymer represented by the following chemical structure: . [0194] As used in Table 3, the term “PNB-TAc-TRZ-5,” where x is 0.05, refers to the TADF polymer represented by the following chemical structure: . [0195] H. Stretchability of Films of PDKCM, PDKCP, PDKCH, and PDKCD. [0196] The stretchability of films of the four exemplary stretchable light-emitting polymers PDKCM, PDKCP, PDKCH, PDKCD was tested by measuring the stretching-induced evolution of luminescent performance up to 100% strain. Consistently with the trends for mechanical properties of the four exemplary stretchable light-emitting polymers illustrated by FIG.16, the crack sizes and crack densities of films under large strains greatly reduced as the alkylene chain length of the exemplary stretchable light-emitting polymer increased, as illustrated by FIGs.27 and 28. For example, a PDKCD film under 100% strain demonstrated intact morphology without any cracks, including nanoscale-sized cracks. [0197] The effects of the strain and consequent crack formations on PL properties of the four exemplary stretchable light-emitting polymers were evaluated. However, PL processes are essentially localized to individual TADF units, so even in the case of crack formation, strain has demonstrated little influence on either PLQYs, as illustrated by FIGs.29 – 32, or transient PL decay behaviors, as illustrated by FIGs.21A – 21E, 22A – 22E, and 33 for all of the four exemplary stretchable light-emitting polymers. [0198] The EL performance of the five exemplary stretchable polymers in OLED devices is also determined by the charge injection and by charge transport. Formation of cracks in the emitter layers of the OLEDs, where the emitter layer includes one of the five exemplary stretchable polymers, may have significant effects on charge injection and charge transport. Each of the five exemplary stretchable polymer films was separately physically transferred onto a rigid device stack to study the effects of crack formation in emitter layers in a conventional OLED device structure, as illustrated by FIG.34. The other layers of the OLED device were deposited by thermal evaporation. An additional layer of polystyrene-block- poly(ethylene-ranbutylene)-block-polystyrene (“SEBS”) and 1,3-bis(N-carbazolyl)benzene (“mCP”) blend in a weight ratio of 1:1 SEBS:mCP was inserted beneath the stretchable light- emitting polymer to increase surface adhesion and facilitate transfer. During stretching to 100% strain, the PDKCD film demonstrated much more stable luminance and current density (illustrated by FIG.35) than the PDKCM film (illustrated by FIG.36). Based on the decrease in current density and luminance with increase in strain observed for the PDKCM film, without being bound by theory, it is believed that negative effects of crack formations in the emitting layer of the OLED including PDKCM film result from the combination of contact deterioration between the cracked emitter and the adjacent electron/hole-transporting layers, and the increase of crack-induced charge tripping in the emitting layer. Representative EL spectrum of an OLED with PTrz-tBuCz as the emitting layer is illustrated in FIG.73 (blue-light emission) and FIG.74 (red-light emission). [0199] Further, the extracted EQEmax values for the PDKCD film, illustrated by FIG. 37, decrease negligibly during stretching to 100% strain, and EQE max is maintained at approximately 10%. With repeated stretching to 100% strain for 100 cycles, PDKCD film also exhibits much more stable performance than PDKCM, as illustrated by FIG.38. Compared to known stretchable light-emitting polymers, which have been based on a first-generation FL emitter, as illustrated in FIG. 39, the stretchable light-emitting polymers of the present disclosure achieved substantial increases both in EL efficiency, to twice of the theoretical limit of FL emitters, as represented by EQEmax, and in stretchability, based on crack onset strain. An EQE-current density plot from the OLED with a PTrz-tBuCz emitting layer, in comparison to an EQE-current density plot from an OLED with a small molecule emitter Trz-tBUCz, is illustrated in FIG. 75. The OLED device structure is ITO/PEDOT:PSS_PFI (60 nm)/PTrz- tBuCz or Trz-tBuCz (30 nm)/TmPyPb (55 nm)LiF (1 nm)/Al. An EQE-current density plot from the OLED with a PTrz-tBuCz_30% TPA-AQ emitting layer, in comparison with that from mCP_30% TPA-AQ is illustrated in FIG.76. The OLED device structure is ITO/PTrz- tBuCz_30% TPA-AQ or mCP_30% TPA-AQ (30 nm)/TmPyPb (55 nm)/LiF (1 nm)/Al. The structure of mCP is: [0200] I. Atomistic Molecular Dynamics (MD) Simulations [0201] Atomistic MD simulations were performed to obtain molecular-level insight into the mechanism for strain energy dissipation and correlation of dissipation with the EL process. By tracking the conformation of a randomly selected polymer chain in a modeled PDKCD film, it was demonstrated in FIG.40 that the applied stretching induces the polymer chain to gradually orient toward the stretching direction, which generally dissipates strain. At a detailed level, it was confirmed that the C 10 alkylene units in the PDKCD backbone provide the most significant contribution to strain dissipation. The evolution of the straight-line distances between the terminal atoms for individual alkylene units, and for TADF segments, under stretching to 100% strain were separately evaluated, and it was demonstrated in FIGs. 41A and 41B that the C 10 alkylene chains of stretchable sections of PDKCD are straightened effectively by the applied strain, while the TADF units and the C1alkylene chain of stretchable sections in PDKCM have little conformational change to dissipate strain energy. The intramolecular- conformational structure and the intermolecular-packing structure of the TADF segments for PDKCM, PDKCP, PDKCH, and PDKCD were analyzed and compared, both in the pristine states and under stretching. The intramolecular-conformational structures and intermolecular- packing structures may indicate the influences of the alkylene chains of the stretchable sections and the stretching on the TADF process, the charge transport, and the EL performance. [0202] The distributions of the D-A dihedral angle in TADF units in all four of PDKCM, PDKCP, PDKCH, and PDKCD remained nearly unchanged under strain. The evaluation of the distances and the angles between the first nearest donor-donor (“D-D”) pairs, the first nearest acceptor-acceptor (“A-A”) pairs, and the second-nearest D-A pairs demonstrate very small changes during the stretching process, as illustrated by FIGs.42 to 44. The consistency in the packing structure of PDKCM, PDKCP, PDKCH, and PDKCD is reflected in the radial distribution function of donor and acceptor results, as illustrated in FIGs.45 and 46. The results indicate that both the inserted alkylene units of the stretchable section of PDKCM, PDKCP, PDKCH, and PDKCD and the applied strain before crack formation exert limited influences on long-range charge-carrier hopping, which provides insight into the experimental observations of the EL performances of PDKCM, PDKCP, PDKCH, and PDKCD. [0203] J. Fully Stretchable OLEDs. [0204] To demonstrate the applicability of the stretchable light-emitting polymers of the present disclosure in examples of fully stretchable OLEDs, a set of materials and a fabrication process for imparting stretchability onto all layers of the OLEDs so as to enable efficient charge injections were developed, as illustrated in FIGs.47 and 48. [0205] Both the cathode and anode are stretchable transparent silver nanowire (“AgNW”) assemblies embedded within a thin layer of thermoplastic polyurethane (“TPU”). The cathode and anode fabrication process is illustrated in FIG.49. The electrodes were then released as stretchable, transparent AgNW/TPU/PDMS electrodes, which provide high conductivity, high stretchability, and moderate transparency, as illustrated in FIGs.50 – 53. [0206] Between the cathode and the stretchable light-emitting polymer, so as to bridge the Fermi level of the AgNW and the lowest-unoccupied molecular orbital (“LUMO”) of the stretchable light-emitting polymer, a stretchable electron injection layer (“EIL”) was designed by blending poly[(9,9-bis(3’-((N,N-dimethyl)-N-ethylammonium)-propyl)- 2,7-fluorene)-alt- 2,7-(9,9-dioctylfluorene)] (“PFN-Br”) with polyethyleneimine ethoxylated (“PEIE”) in a weight ratio of 1:1. Without being bound by theory, it is believed that the PEIE both reduces the work function of the AgNW cathode, as illustrated in FIGs. 54 and 55, and enables the stretchability of this EIL by taking advantage of the low T g of the EIL. The EIL has the stretchability of 60% strain, as illustrated in FIG.56. [0207] Poly[(9,9-bis(3’-((N,N-dimethyl)-N-ethylammonium)-propyl)- 2,7-fluorene)-alt-2,7- (9,9-dioctylfluorene)] (PFN-Br) has the following structural formula:
[0209] Between the anode and the stretchable light-emitting polymer is a stretchable hole transporting layer (“HTL”) formed by mixing poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (“PEDOT:PSS”) with perfluorinated ionomers (“PFI”) in a weight ratio of 5:3. The PFI increases stretchability of the HTL to over 100% strain, as illustrated in FIGs. 57 – 59, and reduces the highest-occupied molecular orbital (“HOMO”) level for more efficient hole injection, as illustrated in FIG.60. [0210] Poly(3,4-ethylenedioxythiophene) (PEDOT) has the following structural formula: [0211] Poly(styrenesulfonate) (PSS) has the following structural formula: [0212] In an example, perfluorinated ionomers (PFI) may have the following structural formula: [0213] For fabrication of the fully stretchable OLED devices including stretchable light- emitting polymers of the present disclosure, the solution-processing compatibility between the layers enables the layer-on-layer direct depositions, enabling better interface adhesions in the device. The resulting stretchable OLED devices may be successfully powered by a commercial 9-volt battery, as illustrated in FIG.61. The performance in the original states demonstrates a record-low turn-on voltage of 4.75 V, as illustrated in FIG.62, and a record-high total EQEmax of 3.3% compared to all of the reported stretchable OLEDs as shown in Table 4 (derived by adding together the emission from the cathode and anode sides, as illustrated in FIG.63). TABLE 4 Performance Comparison of Stretchable OLEDs Including Stretchable Light-Emitting Polymers of the Present Disclosure Compared to Previously Reported Examples a Measured from both anode and cathode sides. b Alternating current. CEmax = maximum current efficiency. LEECs = light-emitting electrochemical cells. LECs = light-emitting capacitors. [0214] The following Table 5 further illustrates a performance comparison of the stretchable light-emitting polymer OLEDs with previously reported stretchable OLEDs and representative stretchable light-emitting electrochemical cells (“LEECs”) and light-emitting capacitors (“LECs”). TABLE 5
a WLEP, white-light-emitting polymer, which was provided by Cambridge Display Company but without specific name offered from the literature. b Measured from both anode and cathode sides. c Total value from both anode and cathode sides. d Alternating current model. Brightness max , maximum luminance value. CE max , maximum current efficiency. TADF- OLEDs, TADF emitter-based OLEDS. FL-OLEDs, fluorescent emitter-based OLEDs. [0215] Compared to the EL performance of the stretchable light-emitting polymers of formula (I), (II), (III), (IV), (V), or (VI) in rigid OLED devices, the lower EQE max of fully stretchable OLEDs including a stretchable light-emitting polymer of formula (I), (II), (III), (IV), (V), or (VI) may result from the lower conductance, non-ideal interface band alignment, and limited transparency and increased resistance of the AgNW electrodes. [0216] The example of the fully stretchable OLED of FIG.47 may be stretched to 60% while keeping the unshifted luminescent wavelength with the CIE chromaticity coordinates of (0.31, 0.53), as illustrated in FIG.64. The luminance of the OLED of FIG.47 maintains at over 60% of its original value, as illustrated in FIG. 65, and the EQE max maintains at over 50% of its original value, as illustrated in FIG. 66. When stretched to over 60% strain, any incidental failures may be attributable to shorting between the AgNW electrodes across the thickness- decreased middle layers. [0217] Although the present disclosure has been described with reference to examples and the accompanying drawings, the present disclosure is not limited thereto, but may be variously modified and altered by those skilled in the art to which the present disclosure pertains without departing from the spirit and scope of the present disclosure. [0218] The subject-matter of the disclosure may also relate, among others, to the following aspects: [0219] A first aspect relates to a stretchable light-emitting polymer of formula (I), (II), (III), (IV), or (V):
wherein D is a donor chemical moiety capable of donating electrons; A is an acceptor chemical moiety capable of accepting electrons; T is a chemical moiety comprising D bonded to A; S is a stretchable section, comprising a stretchable chemical moiety selected from the group consisting of , , m is an integer from 1 to 100; n is an integer from 1 to 50; and a dihedral angle of a bond between D and A is from about 75.0° to about 90.0°. [0220] A second aspect relates to the polymer of aspect 1, wherein the stretchable section comprises a stretchable chemical moiety selected from the group consisting of , , ; and wherein R is a linker moiety, bonded in either direction, selected from the group consisting of , , , , [0221] A third aspect relates to the polymer of any preceding aspect, wherein the donor chemical moiety is selected from the group consisting of: and wherein the donor chemical moiety is bonded to the acceptor chemical moiety at a carbon or nitrogen atom of the donor chemical moiety. [0222] A fourth aspect relates to the polymer of any preceding aspect, wherein the acceptor chemical moiety is selected from the group consisting of:
wherein the acceptor chemical moiety is bonded to the donor chemical moiety at a carbon, nitrogen, boron, or sulfur atom, and the acceptor chemical moiety is bonded to each of two stretchable sections at each of a second and a third carbon, nitrogen, boron, or sulfur atom. [0223] A fifth aspect relates to the polymer of any preceding aspect, wherein the polymer is a polymer of formula (VI):
wherein m is an integer from 1 to 100; and n is an integer from 1 to 50. [0224] A sixth aspect relates to the polymer of any preceding aspect, wherein the polymer is selected from the group consisting of:
[0225] A seventh aspect relates to the polymer of any preceding aspect, wherein the polymer exhibits a charge transfer absorption at a wavelength of from 350 to 400 nanometers, and a second charge transfer absorption at a wavelength of from 400 to 450 nanometers. [0226] An eighth aspect relates to the polymer of any preceding aspect, wherein the polymer hibit t d f b t 10 d d dl d d f b t 3 i d [0227] A ninth aspect relates to the polymer of any preceding aspect, wherein the polymer exhibits a crack on-set strain of greater than 100%. [0228] A tenth aspect relates to a stretchable organic light-emitting diode, comprising: a cathode layer; an anode layer; a film comprising a polymer of any preceding aspect; a stretchable electron injection layer between the cathode layer and the film; and a stretchable hole transporting layer between the anode layer and the film. [0229] An eleventh aspect relates to the diode of aspect 10, wherein the cathode layer and the anode layer comprise thermoplastic polyurethane comprising transparent silver nanowire. [0230] A twelfth aspect relates to the diode of aspects 10 and 11, wherein the electron injection layer comprises poly[(9,9-bis(3’-((N,N-dimethyl)-N-ethylammonium)-propyl)- 2,7-fluorene)- alt-2,7-(9,9-dioctylfluorene)] (PFN-Br) and polyethylene ethoxylated (PEIE) in a weight ratio of from about 2:1 to about 1:4. [0231] A thirteenth aspect relates to the diode of aspects 10 to 12, wherein the hole transporting layer comprises poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) with perfluorinated ionomers (PFI) in a weight ratio of from about 3:1 to about 1:50. [0232] A fourteenth aspect relates to the diode of aspects 10 to 13, wherein the diode is configured to exhibit a maximum external quantum efficiency of about 10% during stretching to 100% strain. [0233] A fifteenth aspect relates to the diode of aspects 10 to 14, wherein the diode is configured to exhibit a maximum external quantum efficiency of about 3.3% during stretching to 60% strain. [0234] In addition to the features mentioned in each of the independent aspects enumerated above, some examples may show, alone or in combination, the optional features mentioned in the dependent aspects and/or as disclosed in the description above and shown in the figures.