Carbazole-based non-fullerene electron acceptor useful as an organic power generating material and composition thereof

Abstract

Compounds of formula Ia and Ib: (Ia)(Ib), wherein R, R1, and R2 are each independently a linear or branched C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, and T1 and T2 are each independently =O, =C(CN)2, or =CHCN. Also disclosed are organic photovoltaics (OPVs) based on binary and ternary compositions comprising compounds of Formula Ia and / or Ib. In one embodiment, a compound of Formula Ia (electron acceptor material A1) was combined with PTB7-Th (electron donor material D1) to form a binary bulk heterojunction blend. In one embodiment, a pair of compounds of Formula Ia (electron acceptor material A1) was combined with PTB7-Th (electron donor material D1) to form a ternary bulk heterojunction blend. In a further embodiment, a compound of Formula Ib (electron acceptor material A1) was combined with P3HT (electron donor material D1) to form a binary bulk heterojunction blend. [Formula 1] TIFF2025527436000115.tif45170

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 63 / 373,785, filed August 29, 2022. The contents of the referenced application are incorporated herein by reference.

[0002] The present disclosure relates generally to novel organic power-generating materials and uses thereof. More specifically, but not exclusively, the present disclosure relates to novel blends for low-intensity indoor light collection. Even more specifically, but not exclusively, the present disclosure relates to novel organic power-generating materials based on binary or ternary bulk heterojunction (BHJ) blends. The present disclosure also relates to processes for the preparation of novel organic power-generating materials based on binary or ternary bulk heterojunction (BHJ) blends. Furthermore, the present disclosure relates to the use of the novel organic power-generating materials in organic electronics. [Background technology]

[0003] Indoor photovoltaics (iPV) aims to concentrate artificial light and is expected to play a key role as a power source for Internet of Things (IoT) systems. One of the immediate market entry points for iPV is powering small electronic devices, and tens of billions of these devices are expected to be installed within the next decade. Indoor light intensities in the range of 500 lux (office space) and 1000 lux (factory) are sufficient to provide over 100 μW of power using small iPV modules. This power is sufficient to power smart IoT devices such as radio frequency identification (RFID) tags (approximately 10 μW), Ecobee thermostats (approximately 18 μW), and passive WiFi (approximately 60 μW). Key to iPV deployment are: i) bandgap design of the active layer—using photoactive materials with a medium bandgap (light absorption in the visible range) to match the emission of LED lighting; and ii) high V to offset voltage losses under low light intensities. oc value, [1] and iii) large-scale device performance review.

[0004] The incorporation of non-fullerenes as electron acceptors into organic solar cells (OSCs) has contributed significantly to increasing the power conversion efficiency (PCE) by up to 30% in certain cases by capturing more solar energy. The general design of these non-fullerene-containing materials typically involves a conjugated ADA structure. Carbazole- and indolocarbazole-based non-fullerenes have been investigated. [2、3] The near-term goal for the structural design is to reach and exceed a PCE of 20%. [4] Recent research has shown that AM (AirMass) 1.5

[15] at 17.1% [5、6] , 17.2% [7、8] , 17.48% [9] , 17.6% [10、11] , 17.7%

[12] , 18.01%

[13] , 18.16%

[14] and a PCE of 18.38% have been reported. Furthermore, a PCE of 20.73% was recently reported for a carbazole-based non-fullerene at 1000 lux and 3000 K.

[16]

[0005] Carbazole-based DA nonfullerenes have also been investigated, but the reported PCEs have generally been moderate (Figure 1). [17~19] To that effect, (DA)1 was shown to offer the best performance, with a PCE of 9.29%, which is surprising in view of the N-substituted carbazole (DA) derivatives (D = N-phenylcarbazole; A = 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile and 2-(1,3-dihydro-1,3-dioxo-2H-inden-2-ylidene) that exhibit rather low electric field-induced second order high wavelength (EFISH) β values.

[20] This suggests that the charge transfer process is not so extensive as to make these molecules unsuitable as non-fullerene acceptors.

[0006] Novel carbazole-based non-fullerene electron acceptors that provide improved PCE values ​​are of commercial interest. Additionally, binary and ternary blends that include such novel carbazole-based non-fullerene electron acceptors, and devices based on such blends, are of commercial interest. Summary of the Invention

[0007] The present disclosure relates generally to novel organic power-generating materials and uses thereof. More specifically, but not exclusively, the present disclosure relates to novel blends for low-intensity indoor light collection. Even more specifically, but not exclusively, the present disclosure relates to novel organic power-generating materials based on binary or ternary bulk heterojunction (BHJ) blends. The present disclosure also relates to processes for the preparation of novel organic power-generating materials based on binary or ternary bulk heterojunction (BHJ) blends. Furthermore, the present disclosure relates to the use of the novel organic power-generating materials in organic electronics.

[0008] Solutions have been discovered to the problems associated with developing new, cost-effective compounds suitable for use in OPV devices. Broadly, the solutions reside in the discovery of novel carbazole-based non-fullerenes suitable for use in OPV devices. In one aspect, the disclosure relates to binary blends comprising an electron donor material and an electron acceptor material. In a further aspect, the disclosure relates to ternary blends comprising an electron donor material and at least two electron acceptor materials. In a further aspect, the disclosure relates to binary blends comprising an electron donor material and a carbazole-based non-fullerene electron acceptor material. In a further aspect, the disclosure relates to ternary blends comprising an electron donor material and first and second carbazole-based non-fullerene electron acceptor materials. These binary and ternary blends can be advantageously used in OPVs for efficient indoor light collection.

[0009] In one aspect, the disclosure provides a compound of formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.

[0010] In one aspect, the present disclosure provides a compound of formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.

[0011] In one aspect, the present disclosure provides a composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.

[0012] In one aspect, the present disclosure provides a composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15-alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.

[0013] In one aspect, the present disclosure provides a composition comprising at least two electron acceptor materials A1 and A2 and at least one electron donor material D1, wherein the electron acceptor materials A1 and A2 are of formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.

[0014] In one aspect, the present disclosure provides a composition comprising at least two electron acceptor materials A1 and A2 and at least an electron donor material D1, wherein the electron acceptor materials A1 and A2 are of formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.

[0015] In one aspect, the present disclosure provides a composition comprising at least two electron acceptor materials A1 and A2 and at least one electron donor material D1, wherein the electron acceptor materials A1 and A2 are of formula Ia and / or Ib: [ka] wherein R, R1, and R2 are each independently a linear or branched C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.

[0016] In one embodiment of the present disclosure, the mass ratio (w / w) of the acceptor material(s) to the donor material can be about 0.5:1.0 to about 1.0:0.5, such as about 0.6:0.9 to about 0.9:0.6, such as about 0.7:0.8 to about 0.8:0.7, or any range derivable therein, such as about 0.75:0.75. In certain embodiments, binary blends comprise an acceptor:donor ratio (w / w) of about 0.5:1.0 to about 1.0:0.5. In certain embodiments, ternary blends comprise an acceptor:donor ratio (w / w) of about 0.5:1.0 to about 1.0:0.5. In further embodiments of the present disclosure, binary and ternary blends can be slot-die coated from environmentally friendly solvents (e.g., halogen-free solvents).

[0017] In one aspect, the present disclosure provides a binary composition exhibiting a bandgap sufficiently matched to a complete indoor LED emission spectrum, the composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.

[0018] In one aspect, the present disclosure provides a binary composition exhibiting a bandgap sufficiently matched to a complete indoor LED emission spectrum, the composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.

[0019] In one aspect, the present disclosure provides a ternary composition exhibiting a bandgap sufficiently matched to a complete indoor LED emission spectrum, the composition comprising at least two electron acceptor materials A1 and A2 and at least an electron donor material D1, wherein the electron acceptor materials A1 and A2 are of Formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.

[0020] In one aspect, the present disclosure provides a ternary composition exhibiting a bandgap sufficiently matched to a complete indoor LED emission spectrum, the composition comprising at least two electron acceptor materials A1 and A2 and at least an electron donor material D1, wherein the electron acceptor materials A1 and A2 are of Formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.

[0021] In one aspect, the present disclosure provides a ternary composition exhibiting a bandgap sufficiently matched to a complete indoor LED emission spectrum, the composition comprising at least two electron acceptor materials A1 and A2 and at least an electron donor material D1, wherein the electron acceptor materials A1 and A2 are of formula Ia and / or Ib: [ka] wherein R, R1, and R2 are each independently a linear or branched C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.

[0022] In one aspect, the present disclosure provides a binary composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; T1 and T2 are each independently =O, =C(CN)2, or =CHCN; and the electron donor material D1 can be PTB7-Th (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})).

[0023] In one aspect, the present disclosure provides a ternary composition comprising two electron acceptor materials A1 and A2 and at least an electron donor material D1, wherein the electron acceptor materials A1 and A2 are of formula Ia: [ka] In the formula, R is a linear or branched chain C6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; T1 and T2 are each independently =O, =C(CN)2, or =CHCN; and the electron donor material D1 can be PTB7-Th (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})).

[0024] In one aspect, the present disclosure provides a binary composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; T1 and T2 are each independently =O, =C(CN)2, or =CHCN; and the electron donor material D1 can be poly(3-hexylthiophene) (P3HT).

[0025] In one aspect, the present disclosure provides a ternary composition comprising two electron acceptor materials A1 and A2 and at least an electron donor material D1, wherein the electron acceptor materials A1 and A2 are of formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; T1 and T2 are each independently =O, =C(CN)2, or =CHCN; and the electron donor material D1 can be poly(3-hexylthiophene) (P3HT).

[0026] In one aspect, the present disclosure relates to a photoactive layer for an iOPV (indoor organic photovoltaic) structure having high thermal stability and strong visible light absorption. In one embodiment, the photoactive layer comprises a binary composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of Formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, T1 and T2 are each independently =O, =C(CN)2, or =CHCN, and the electron donor material D1 can be PTB7-Th (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})).

[0027] In one aspect, the present disclosure relates to a photoactive layer for an iOPV (indoor organic photovoltaic) structure having high thermal stability and strong visible light absorption. In one embodiment, the photoactive layer comprises a ternary composition comprising two electron acceptor materials A1 and A2 and at least one electron donor material D1, wherein the electron acceptor materials A1 and A2 are of Formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, T1 and T2 are each independently =O, =C(CN)2, or =CHCN, and the electron donor material D1 can be PTB7-Th (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})).

[0028] In one aspect, the present disclosure relates to a photoactive layer for an iOPV (indoor organic photovoltaic) structure having high thermal stability and strong visible light absorption. In one embodiment, the photoactive layer comprises a binary composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of Formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, T1 and T2 are each independently =O, =C(CN)2, or =CHCN, and the electron donor material D1 can be poly(3-hexylthiophene) (P3HT).

[0029] In one aspect, the present disclosure relates to a photoactive layer for an iOPV (indoor organic photovoltaic) structure having high thermal stability and strong visible light absorption. In one embodiment, the photoactive layer comprises a ternary composition comprising two electron acceptor materials A1 and A2 and at least one electron donor material D1, wherein the electron acceptor materials A1 and A2 are of formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, T1 and T2 are each independently =O, =C(CN)2, or =CHCN, and the electron donor material D1 can be poly(3-hexylthiophene) (P3HT).

[0030] In one aspect, the present disclosure relates to the use of a binary composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15-alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, T1 and T2 are each independently =O, =C(CN)2, or =CHCN, and the electron donor material D1 can be PTB7-Th (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})) to improve device photocurrent generation. In one embodiment of the present disclosure, the device is an OPV used for indoor light recycling.

[0031] In one aspect, the present disclosure relates to the use of a ternary composition comprising two electron acceptor materials A1 and A2 and at least an electron donor material D1, wherein the electron acceptor materials A1 and A2 are of formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, T1 and T2 are each independently =O, =C(CN)2, or =CHCN, and the electron donor material D1 can be PTB7-Th (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})) to improve device photocurrent generation. In one embodiment of the present disclosure, the device is an OPV used for indoor light recycling.

[0032] In one aspect, the present disclosure relates to the use of a binary composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15-alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, T1 and T2 are each independently =O, =C(CN)2, or =CHCN, and the electron donor material D1 can be poly(3-hexylthiophene) (P3HT) to enhance device photocurrent generation. In one embodiment of the present disclosure, the device is an OPV used for indoor light recycling.

[0033] In one aspect, the present disclosure relates to the use of a ternary composition comprising two electron acceptor materials A1 and A2 and at least an electron donor material D1, wherein the electron acceptor materials A1 and A2 are of formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, T1 and T2 are each independently =O, =C(CN)2, or =CHCN, and the electron donor material D1 can be poly(3-hexylthiophene) (P3HT) to enhance device photocurrent generation. In one embodiment of the present disclosure, the device is an OPV used for indoor light recycling.

[0034] In one aspect, the present disclosure relates to the use of a binary composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15-alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, T1 and T2 are each independently =O, =C(CN)2, or =CHCN, and the electron donor material D1 can be PTB7-Th (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})) as an organic semiconductor material, layer, or component.

[0035] In one aspect, the present disclosure relates to the use of a ternary composition comprising two electron acceptor materials A1 and A2 and at least an electron donor material D1, wherein the electron acceptor materials A1 and A2 are of formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, T1 and T2 are each independently =O, =C(CN)2, or =CHCN, and the electron donor material D1 can be PTB7-Th (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})) as an organic semiconductor material, layer, or component.

[0036] In one aspect, the present disclosure relates to the use of a binary composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15-alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, T1 and T2 are each independently =O, =C(CN)2, or =CHCN, and the electron donor material D1 may be poly(3-hexylthiophene) (P3HT) as an organic semiconductor material, layer, or component.

[0037] In one aspect, the present disclosure relates to the use of a ternary composition comprising two electron acceptor materials A1 and A2 and at least an electron donor material D1, wherein the electron acceptor materials A1 and A2 are of formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, T1 and T2 are each independently =O, =C(CN)2, or =CHCN, and the electron donor material D1 may be poly(3-hexylthiophene) (P3HT) as an organic semiconductor material, layer, or component.

[0038] In one aspect, the present disclosure provides an organic solar cell comprising an anode and a cathode and a photoactive layer between the anode and the cathode, wherein the photoactive layer comprises an electron donor / acceptor material, and the electron acceptor material is of Formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, T1 and T2 are each independently =O, =C(CN)2, or =CHCN, and the electron donor material D1 can be PTB7-Th (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})).

[0039] In one aspect, the present disclosure provides an organic solar cell comprising an anode and a cathode and a photoactive layer between the anode and the cathode, wherein the photoactive layer comprises an electron donor / acceptor material, and the electron acceptor material is of Formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; T1 and T2 are each independently =O, =C(CN)2, or =CHCN; and the electron donor material D1 can be poly(3-hexylthiophene) (P3HT).

[0040] In one aspect, the present disclosure includes a composition of matter, an electronic device comprising a heterojunction, the heterojunction comprising an electron donor and an electron acceptor material, the electron acceptor material being of Formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; T1 and T2 are each independently =O, =C(CN)2, or =CHCN; and the electron donor material D1 can be PTB7-Th (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})). In one embodiment of the present disclosure, the electronic device is an OPV device. In a further embodiment of the present disclosure, the OPV is used for indoor light collection.

[0041] In one aspect, the present disclosure includes a composition for an electronic device comprising a heterojunction, the heterojunction comprising two electron acceptor materials A1 and A2 and at least an electron donor material D1, wherein the electron acceptor materials A1 and A2 are of Formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; T1 and T2 are each independently =O, =C(CN)2, or =CHCN; and the electron donor material D1 can be PTB7-Th (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})). In one embodiment of the present disclosure, the electronic device is an OPV device. In a further embodiment of the present disclosure, the OPV is used for indoor light collection.

[0042] In one aspect, the present disclosure includes a composition for an electronic device comprising a heterojunction, the heterojunction comprising an electron donor and an electron acceptor material, the electron acceptor material being of Formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; T1 and T2 are each independently =O, =C(CN)2, or =CHCN; and the electron donor material D1 can be poly(3-hexylthiophene) (P3HT). In one embodiment of the present disclosure, the electronic device is an OPV device. In a further embodiment of the present disclosure, the OPV is used for indoor light collection.

[0043] In one aspect, the present disclosure includes a composition for an electronic device comprising a heterojunction, the heterojunction comprising two electron acceptor materials A1 and A2 and at least an electron donor material D1, wherein the electron acceptor materials A1 and A2 are of Formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; T1 and T2 are each independently =O, =C(CN)2, or =CHCN; and the electron donor material D1 can be poly(3-hexylthiophene) (P3HT). In one embodiment of the present disclosure, the electronic device is an OPV device. In a further embodiment of the present disclosure, the OPV is used for indoor light collection.

[0044] In one aspect, the disclosure relates to compounds of the formula: [ka]

[0045] In one aspect, the disclosure relates to compounds of the formula: [ka]

[0046] In one aspect, the disclosure relates to compounds of the formula: [ka]

[0047] Also disclosed in the context of this disclosure are embodiments 1-93. Embodiment 1 is a compound of Formula Ia, [ka] In the formula, R is a linear or branched chain C 6-15-alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, and T1 and T2 are each independently =O, =C(CN)2, or =CHCN. [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl, and X1, X2, X3, and X4 are each independently H, F, Cl, or Br. Embodiment 3 is a compound of embodiment 1, comprising the structure of formula IIIa: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl, and X1, X2, X3, and X4 are each independently H, F, Cl, or Br. [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl and X1, X2, X3, and X4 are each independently H, F, Cl, or Br. Embodiment 5 is a compound of any one of Embodiments 2-4, where X1, X2, X3, and X4 are each independently H. Embodiment 6 is a compound of Embodiment 5, where R is 2-ethylhexyl.

[0048] Embodiment 7 is a compound of formula Ib, [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, and T1 and T2 are each independently =O, =C(CN)2, or =CHCN. [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl, and X1, X2, X3, and X4 are each independently H, F, Cl, or Br. Embodiment 9 is a compound of embodiment 7, comprising the structure of formula IIIb: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl. Embodiment 10 is a compound of embodiment 8, comprising the structure of formula IVb: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl. Embodiment 11 is a compound of any one of embodiments 7-10, wherein R is 2-ethylhexyl.

[0049] Embodiment 12 is a composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, and T1 and T2 are each independently =O, =C(CN)2, or =CHCN. [ka] In the formula, R is a linear or branched chain C 6-15-alkyl, and X1, X2, X3, and X4 are each independently H, F, Cl, or Br.Embodiment 14 is the composition of embodiment 12, wherein the electron acceptor material A1 has the structure of formula IIIa: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl, and X1, X2, X3, and X4 are each independently H, F, Cl, or Br.Embodiment 15 is the composition of embodiment 12, wherein the electron acceptor material A1 has the structure of formula IVa: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl and X1, X2, X3, and X4 are each independently H, F, Cl, or Br. Embodiment 16 is the composition of any one of Embodiments 12-15, wherein X1, X2, X3, and X4 are each independently H. Embodiment 17 is the composition of Embodiment 16, wherein R is 2-ethylhexyl.

[0050] Embodiment 18 is a composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, and T1 and T2 are each independently =O, =C(CN)2, or =CHCN. [ka] wherein R1 and R2 are each independently a linear or branched C 6-15-alkyl, and X1, X2, X3, and X4 are each independently H, F, Cl, or Br.Embodiment 20 is the composition of embodiment 18, wherein electron acceptor material A1 has the structure of formula IIIb: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl. Embodiment 21 is the composition of embodiment 18, wherein the electron acceptor material A1 has the structure of formula IVb: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15-alkyl. Embodiment 22 is the composition of any one of Embodiments 18-21, wherein R is 2-ethylhexyl. Embodiment 23 is the composition of any one of Embodiments 12-22, wherein electron donor material D1 comprises a p-type organic semiconductor material. Embodiment 24 is the composition of any one of Embodiments 12-22, wherein electron donor material D1 comprises a p-type organic semiconductor material, such as (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})) (PTB7-Th), poly(3-hexylthiophene) (P3HT), poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt

[0039] Embodiment 25 is the composition of any one of embodiments 12 to 24, wherein the composition comprises a weight ratio (w / w) of acceptor material to donor material ranging from about 0.5:1.0 to about 1.0:0.5.

[0040] Embodiment 26 is the composition of any one of embodiments 12 to 25, wherein the composition is slot-die coated.

[0041] Embodiment 27 is the composition of any one of embodiments 12 to 25, wherein the composition is spin-coated. Embodiment 28 is the composition of any one of embodiments 12 to 27, wherein the composition produces a bandgap suitable for low intensity light concentration, and the blend has significant absorption of visible light between 380 nm and 940 nm suitable for low intensity light concentration.Embodiment 29 is the composition of any one of embodiments 12 to 28, wherein the composition is provided in the form of a bulk material or a film.

[0051] Embodiment 30 is a composition comprising at least two electron acceptor materials A1 and A2 and at least an electron donor material D1, wherein the electron acceptor materials A1 and A2 are of Formula Ia: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.Embodiment 31 is a composition wherein at least one of the two electron acceptor materials A1 and A2 has a structure of Formula IIa: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl, and X1, X2, X3, and X4 are each independently H, F, Cl, or Br.Embodiment 32 is the composition of embodiment 30, wherein at least one of the two electron acceptor materials A1 and A2 has the structure of Formula IIIa: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl, and X1, X2, X3, and X4 are each independently H, F, Cl, or Br.Embodiment 33 is the composition of embodiment 30, wherein at least one of the two electron acceptor materials A1 and A2 has the structure of Formula IVa: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl and X1, X2, X3, and X4 are each independently H, F, Cl, or Br. Embodiment 34 is the composition of any one of Embodiments 30-33, wherein X1, X2, X3, and X4 are each independently H. Embodiment 35 is the composition of Embodiment 34, wherein R is 2-ethylhexyl.

[0052] Embodiment 36 is a composition comprising at least two electron acceptor materials A1 and A2 and at least an electron donor material D1, wherein the electron acceptor materials A1 and A2 are of Formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.Embodiment 37 is a composition wherein at least one of the two electron acceptor materials A1 and A2 has the structure of Formula IIb: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl, and X1, X2, X3, and X4 are each independently H, F, Cl, or Br.Embodiment 38 is the composition of embodiment 36, wherein at least one of the two electron acceptor materials A1 and A2 has the structure of Formula IIIb: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl. Embodiment 39 is the composition of embodiment 36, wherein at least one of the two electron acceptor materials A1 and A2 has the structure of formula IVb: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15-alkyl. Embodiment 40 is the composition of any one of Embodiments 36-39, wherein R is 2-ethylhexyl. Embodiment 41 is the composition of any one of Embodiments 30-40, wherein electron donor material D1 comprises a p-type organic semiconductor material. Embodiment 42 is the composition of any one of Embodiments 36-39, wherein electron donor material D1 comprises a p-type organic semiconductor material.

[0049] Embodiment 43 is the composition of any one of embodiments 30-42, wherein the composition comprises a mass ratio (w / w) of acceptor material to donor material ranging from about 0.5:1.0 to about 1.0:0.5.

[0050] Embodiment 44 is the composition of any one of embodiments 30-43, wherein the composition is slot-die coated.

[0051] Embodiment 45 is the composition of any one of embodiments 30-43, wherein the composition is spin-coated. Embodiment 46 is the composition of any one of embodiments 30 through 45, wherein the composition produces a bandgap suitable for low intensity light concentration, and the blend has significant absorption of visible light between 380 nm and 940 nm suitable for low intensity light concentration.Embodiment 47 is the composition of any one of embodiments 30 through 46, wherein the composition is provided in the form of a bulk material or a film.

[0053] Embodiment 48 is a composition comprising at least two electron acceptor materials A1 and A2 and at least one electron donor material D1, wherein the electron acceptor materials A1 and A2 are of formula Ia and / or Ib: [ka] wherein R, R1, and R2 are each independently a linear or branched C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.Embodiment 49 is a composition wherein at least one of the two electron acceptor materials A1 and A2 has the structure of Formula IIa: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl, and X1, X2, X3, and X4 are each independently H, F, Cl, or Br.Embodiment 50 is the composition of embodiment 48, wherein at least one of the two electron acceptor materials A1 and A2 has the structure of Formula IIIa: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl, and X1, X2, X3, and X4 are each independently H, F, Cl, or Br.Embodiment 51 is the composition of embodiment 48, wherein at least one of the two electron acceptor materials A1 and A2 has the structure of Formula IVa: [ka] In the formula, R is a linear or branched chain C 6-15 -alkyl, and X1, X2, X3, and X4 are each independently H, F, Cl, or Br.Embodiment 52 is the composition of embodiment 48, wherein at least one of the two electron acceptor materials A1 and A2 has the structure of Formula IIb: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15-alkyl, and X1, X2, X3, and X4 are each independently H, F, Cl, or Br.Embodiment 53 is the composition of embodiment 48, wherein at least one of the two electron acceptor materials A1 and A2 has the structure of Formula IIIb: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15 -alkyl.Embodiment 54 is the composition of embodiment 48, wherein at least one of the two electron acceptor materials A1 and A2 has the structure of Formula IVb: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15-alkyl. Embodiment 55 is the composition of any one of Embodiments 48 through 54, wherein electron donor material D1 comprises a p-type organic semiconductor material. Embodiment 56 is the composition of any one of Embodiments 48 through 54, wherein electron donor material D1 comprises a p-type organic semiconductor material selected from the group consisting of (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})) (PTB7-Th), poly(3-hexylthiophene) (P3HT), poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt 57 is the composition of any one of embodiments 48-56, wherein the composition comprises a mass ratio (w / w) of acceptor material to donor material ranging from about 0.5:1.0 to about 1.0:0.5. Embodiment 58 is the composition of any one of embodiments 48-57, wherein the composition is slot-die coated. Embodiment 59 is the composition of any one of embodiments 48-57, wherein the composition is spin-coated. Embodiment 60 is the composition of any one of embodiments 48-59, wherein the composition produces a bandgap suitable for low intensity light concentration, and the blend has significant absorption of visible light between 380 nm and 940 nm suitable for low intensity light concentration.Embodiment 61 is the composition of any one of embodiments 48-60, wherein the composition is provided in the form of a bulk material or a film.

[0054] Embodiment 62 is the use of a compound as defined in any one of embodiments 1 to 11 as an electron acceptor compound.

[0055] Embodiment 63 is an organic solar cell comprising an anode and a cathode and a photoactive layer between the anode and the cathode, wherein the photoactive layer comprises an electron donor / acceptor material, and the electron acceptor material is as defined in any one of embodiments 1 to 11. Embodiment 64 is the organic solar cell of embodiment 63, wherein the electron donor material comprises a p-type organic semiconductor material. Embodiment 65 is the organic solar cell of embodiment 63, wherein the electron donor material is selected from the group consisting of (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})) (PTB7-Th), poly(3-hexylthiophene) (P3HT), poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt

[0039] Embodiment 66 is the organic solar cell of any one of embodiments 63 to 65, wherein the photoactive layer comprises a weight ratio (w / w) of acceptor material to donor material ranging from about 0.5:1.0 to about 1.0:0.5. Embodiment 67 is the organic solar cell of any one of embodiments 63 to 66, wherein the photoactive layer is slot-die coated. Embodiment 68 is the organic solar cell of any one of embodiments 63 to 66, wherein the photoactive layer is spin-coated. Embodiment 69 is the organic solar cell of any one of embodiments 63 to 68, wherein one of the cathode and the anode comprises one of indium tin oxide (ITO), indium-doped zinc oxide (IZO), tin oxide (SnO), aluminum-doped zinc oxide (AZO), or gallium-doped zinc oxide (GZO), and the other of the cathode and the anode comprises one of aluminum (Al), silver (Ag), gold (Au), or lithium (Li).Embodiment 70 is the organic solar cell of any one of embodiments 63 to 69, wherein the photoactive layer produces a bandgap suitable for low-intensity light concentration, and the photoactive layer has significant absorption of visible light between 380 nm and 940 nm suitable for low-intensity light concentration.Embodiment 71 is the organic solar cell of any one of embodiments 63 to 70, wherein the photoactive layer is provided in the form of a bulk material or a film.

[0056] Embodiment 72 is an electronic device comprising a heterojunction, the heterojunction comprising a blend comprising an electron donor and an electron acceptor material, the electron acceptor material being as defined in any one of embodiments 1 to 11. Embodiment 73 is the electronic device of embodiment 72, wherein the electron donor material comprises a p-type organic semiconductor material. Embodiment 74 is the electronic device of embodiment 72, wherein the electron donor material comprises a p-type organic semiconductor material, such as (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})) (PTB7-Th), poly(3-hexylthiophene) (P3HT), poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt

[0049] Embodiment 75 is the electronic device of any one of embodiments 72 to 74, wherein the heterojunction comprises a mass ratio (w / w) of acceptor material to donor material ranging from about 0.5:1.0 to about 1.0:0.5. Embodiment 76 is the electronic device of any one of embodiments 72 to 75, wherein the blend is slot-die coated. Embodiment 77 is the electronic device of any one of embodiments 72 to 75, wherein the blend is spin-coated. Embodiment 78 is the electronic device of any one of embodiments 72 to 77, wherein the blend produces a bandgap suitable for low-intensity light collection, and the blend has significant absorption of visible light between 380 nm and 940 nm suitable for low-intensity light collection. Embodiment 79 is the electronic device of any one of embodiments 72 to 78, wherein the blend is provided in the form of a bulk material or a film. Embodiment 80 is the electronic device of embodiment 72, wherein the device is a photovoltaic cell, an organic transistor, a light-emitting diode, or a photodetector.

[0057] Embodiment 81 is an organic semiconductor material, layer, or component comprising the composition defined in any one of embodiments 12 to 29. Embodiment 82 is an organic semiconductor material, layer, or component comprising the composition defined in any one of embodiments 30 to 47. Embodiment 83 is an organic semiconductor material, layer, or component comprising the composition defined in any one of embodiments 48 to 61.

[0058] Embodiment 84 is the use of a composition as defined in any one of embodiments 12 to 29 as an organic semiconductor material, layer, or component. Embodiment 85 is the use of a composition as defined in any one of embodiments 30 to 47 as an organic semiconductor material, layer, or component. Embodiment 86 is the use of a composition as defined in any one of embodiments 48 to 61 as an organic semiconductor material, layer, or component. Embodiment 87 is the use of a composition as defined in any one of embodiments 12 to 29 in an electronic device. Embodiment 88 is the use of a composition as defined in any one of embodiments 30 to 47 in an electronic device. Embodiment 89 is the use of a composition as defined in any one of embodiments 48 to 61 in an electronic device. Embodiment 90 is the use of any one of embodiments 84 to 86, wherein the electronic device is a photovoltaic cell, an organic transistor, a light-emitting diode, or a photodetector.

[0059] Embodiment 91 is a bulk heterojunction (BHJ) formed from the composition defined in any one of embodiments 12 to 29. Embodiment 92 is a bulk heterojunction (BHJ) formed from the composition defined in any one of embodiments 30 to 47. Embodiment 93 is a bulk heterojunction (BHJ) formed from the composition defined in any one of embodiments 48 to 61.

[0060] The foregoing and other advantages and features of the present disclosure will become more apparent upon reading the following non-restrictive description of illustrative embodiments thereof, given by way of example only with reference to the accompanying drawings / figures. [Brief explanation of the drawings]

[0061] [Figure 1] Illustrating the chemical structures of various prior art carbazole-based non-fullerenes exhibiting the DA general structure, density functional theory (DFT) calculations confirmed the DA, rather than ADA, nature of the non-fullerenes (DA)2 and (DA)3. [Figure 2] 1 illustrates the chemical structures of electron acceptor materials A1 (MCz and MCzM) according to embodiments of the present disclosure. [Figure 3] 1 illustrates an ORTEP representation (A) of electron acceptor material A1(MCz) according to one embodiment of the present disclosure, and crystal packing (B) along the c-axis showing the spatial arrangement of each single stacked molecule, where the crystal packing exhibits a stepped configuration in which the molecules are arranged face-to-face and adopt a head-to-tail orientation. [Figure 4] 1 illustrates a cyclic voltammogram (scan rate=50 mV / s) of electron acceptor material A1 (MCz) in CH2Cl2 (A) and an energy diagram illustrating the HOMO and LUMO energies of MCz and PTB7-Th (based on Eox onset and Ered onset values) according to one embodiment of the present disclosure (B). [Figure 5] Illustrates the absorption, emission, and excitation spectra of electron acceptor material A1 (MCz) according to one embodiment of the present disclosure: top left: in DCM at 298 K, top right: in 2-MeTHF at 298 K, bottom left: in the solid state at 298 K, and bottom right: in 2-MeTHF at 77 K. The absorptivity of MCz at 520 nm is 46700 M-1 cm-1. [Figure 6] 1 illustrates the molecular orbital representation (H=HOMO, L=LUMO) of the frontier orbitals of electron acceptor material A1 (MCz) using solvent field CH2Cl2 according to one embodiment of the present disclosure. [Figure 7]1 illustrates a simulated absorption spectrum of electron acceptor material A1 (MCz) using time-dependent density functional theory (TDDFT) calculations according to one embodiment of the present disclosure. The bar graph below the absorption spectrum illustrates the calculated oscillator strengths (f) and calculated positions of the first 100 electronic transitions for MCz. An arbitrary thickness of 1000 cm is assigned to each bar to generate the simulated spectrum. [Figure 8] Illustrates: (A) Emission decay of MCz in 2-MeTHF at 298 K (emission decay; residuals; instrument response function (IRF); and best fit); multiexponential analysis gives τ = 0.25 μs (16.2%), 1.67 μs (83.8%); χ = 1.08; inset, multiexponential analysis; λ = 477 nm. (B) Emission decay of MCz in 2-MeTHF at 77 K (emission decay; residuals; instrument response function (IRF); and best fit); multiexponential analysis gives τ = 3.16 μs (100%); χ = 1.01; inset, multiexponential analysis; λ = 477 nm. (C) Luminescence decay of MCz in the solid state at 298 K (luminescence decay; residuals; instrument response function (IRF); and best fit); multiexponential analysis gives τ = 0.13 μs (28.77%), 0.46 μs (37.31%), 1.99 μs (33.92%); χ = 1.01; inset, multiexponential analysis; λ = 477 nm. [Figure 9] 1 illustrates the chemical structures of electron acceptor materials A1 (MDCzM-4F and MDCzM-4H) according to an embodiment of the present disclosure. [Figure 10] 1 illustrates the absorption and photoluminescence emission and excitation spectra of MDCzM-4F and P3HT (A), and the absorption and photoluminescence emission and excitation spectra of MDCzM-4H and P3HT (B), according to one embodiment of the present disclosure. [Figure 11]Figure 1 illustrates the photoluminescence quenching of P3HT, MDCzM-4F, and P3HT:MDCzM-4F (1:1) (A); P3HT, MDCzM-4H, and P3HT:MDCzM-4H (1:1) (B), according to one embodiment of the present disclosure. No significant signals (i.e., other than the blank instrument response) were collected for the P3HT:MDCzM-4F (1:1) and P3HT:MDCzM-4H (1:1) blends. There is significant photoluminescence quenching, most likely due to electron transfer, in the P3HT:MDCzM-4F (1:1) and P3HT:MDCzM-4H (1:1) blends, making these donor / acceptor blends good candidates for use in organic solar cells. [Figure 12] 1 illustrates the absorption spectra of a P3HT:MDCzM-4F (1:1) blend (A); and a P3HT:MDCzM-4H (1:1) blend (B), according to embodiments of the present disclosure. [Figure 13] 1 illustrates the photoluminescence attenuation of MDCzM-4F according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0062] Glossary In order to provide a clear and consistent understanding of the terminology used in this disclosure, several definitions are provided below. Furthermore, 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 belongs.

[0063] The words "a" or "an," when used in conjunction with the term "comprising" in the claims and / or specification, unless the content clearly dictates otherwise, may mean "one," but are also consistent with the meanings of "one or more," "at least one," and "one or more." Similarly, the word "another," unless the content clearly dictates otherwise, may mean at least a second or more.

[0064] As used in this specification and claim(s), the words "comprising" (and any form of including, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "include" and "includes"), or "containing" (and any form of containing, such as "contain" and "contains") are inclusive or open-ended and do not exclude additional, unrecited elements or process steps.

[0065] As used in this specification and claim(s), the word "consisting of" and its derivatives are intended to be closed-ended terms specifying the presence of stated features, elements, components, groups, integers, and / or steps, and also to exclude the presence of other unstated features, elements, components, groups, integers, and / or steps.

[0066] As used herein, the term "consisting essentially of" is intended to specify the presence of stated features, elements, components, groups, integers, and / or steps and / or the presence of something that does not materially affect the basic and novel characteristic(s) of those features, elements, components, groups, integers, and / or steps.

[0067] As used herein, the terms "about," "substantially," and "approximately" refer to a reasonable amount of deviation from the modified term such that the end result is not significantly altered. These terms of degree should be interpreted as including a deviation of at least ±1% of the modified term if this deviation does not negate the meaning of the word it modifies.

[0068] As used herein, the term "polymer" generally includes homopolymers and copolymers, such as, but not limited to, block copolymers, random copolymers, and alternating copolymers.

[0069] As used herein, the terms "donor" or "donating" and "acceptor" or "accepting" will be understood to mean an electron donor or electron acceptor, respectively. An "electron donor" will be understood to mean a chemical that donates an electron to an atom of another compound or another group of compounds. An "electron acceptor" will be understood to mean a chemical that accepts an electron transferred from an atom of another compound or another group of compounds.

[0070] As used herein, fill factor (FF) refers to the theoretical (not practically obtainable) power (J se *V oc ) to the actual maximum obtainable power (Pm or Vmp*Jmp) (given as a percentage). FF is therefore given by the equation FF=(Vmp*Jmp) / (J se *V oc ), where Jmp and Vmp represent the current density and voltage, respectively, at the maximum power point (Pm), which is obtained by varying the resistance in the circuit until J*V reaches its maximum value, and J se and V oc and represent the short circuit current and open circuit voltage, respectively. FF is an important parameter in evaluating the performance of solar cells.

[0071] As used herein, open circuit voltage (V oc ) is the difference in potential between the anode and cathode of the device when no external load is connected.

[0072] As used herein, the power conversion efficiency (PCE) of a solar cell is the percentage of power converted from absorbed light to electrical energy. The PCE of a solar cell is calculated as the ratio of input light irradiance (E, W / m) under standard test conditions (STC).2 unit) and the surface area of ​​the solar cell (Ac, m 2 The STC can be calculated by dividing the maximum power point (Pm) by the maximum power (W / m) in units of Watts per square meter. The STC is typically calculated for a temperature of 25°C and an air mass 1.5 (AM.1.5) spectrum of 1000 W / m. 2 This refers to the irradiance of the

[0073] As used herein, the term "active layer" will be understood to mean a blend of electron donor and electron acceptor materials that responds to an excitation.

[0074] As used herein, the term "absorption" will be understood to mean the ability or process by which a material absorbs some or all of the incident light energy.

[0075] As used herein, the term "excitation" will be understood to mean the process by which the energy state of a material is changed using means such as light.

[0076] In one aspect, the present disclosure provides a binary composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of formula Ia: [ka] In the formula, R is a branched chain C 6-15 -alkyl, X1, X2, X3, and X4 are each independently H, F, Cl, or Br, and T1 and T2 are each independently =O, =C(CN)2, or =CHCN. In one embodiment of the present disclosure, the binary composition comprises an MCz:PTB7-Th system. In one embodiment of the present disclosure, the electron acceptor material A1 has the following structure: [ka]

[0077] The use of MCz advantageously provided improved PCE for outdoor (AM=1.5) and indoor (800 lux, 3000 K) applications compared to that reported for the compound illustrated in Figure 1. Remarkably, a PCE of 9.43% was observed for MCz. Surprisingly, by modifying the ethyl group (DA)5 of the 2-ethylhexyl group (MCz), the PCE dramatically improved from 0.01% to 9.43%. MCzM has also been previously investigated and shown to exhibit good OSC performance.

[21] Simplifying the MCzM structure to MCz (Figure 2) surprisingly did not adversely affect the PCE or OSC performance.

[0078] The synthesis of MCz according to one embodiment of the present disclosure is illustrated in Scheme 1. [ka]

[0079] 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile 5 was prepared according to known literature procedures.

[21] Commercially available 1H-indene-1,3(2H)-dione was reacted with malononitrile during a Knoevenagel condensation to give the 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile moiety 5. Concurrently, to increase the solubility of all subsequent compounds, carbazole 1 was alkylated with 2-ethylhexyl bromide 2 in quantitative yield to give the 9-(2-ethylhexyl)-9H-carbazole moiety 3. Subsequently, mono- and bisformylation of 9-(2-ethylhexyl)-9H-carbazole at the 3- and / or 6-positions was carried out. Monoformylated carbazole 4 was separately isolated or prepared by varying the ratio of POCl in DMF, with an isolated yield of approximately 72%. Reaction of monoformylated carbazole 4 with two equivalents of malononitrile 5 gave MCz in 37% isolated yield. Bisformylated carbazole was reacted in a similar manner to prepare MCzM.

[0080] Single crystals suitable for X-ray diffraction were obtained from a hot mixture of acetonitrile / toluene (1:1), followed by slow evaporation over a 3-day period (Figure 3). The X-ray structure reveals a quasi-planar conformation with a dihedral angle of 3.8° created by the average plane of malononitrile and carbazole. This conformation is possible because the N≡CCC≡N moiety is positioned away from the carbazole unit. The 2-ethylhexyl chains are oriented quasi-perpendicular to the carbazole plane, forming an angle of 89.22° between the average chain axis and the carbazole plane. The crystal packing exhibits a stepped configuration, with the molecules positioned face-to-face adopting a head-to-tail orientation. The interplanar separation is 3.380 Å, suggesting good π-π contacts between individual MCz molecules in the solid state.

[0081] Cyclic voltammograms (CVs) of MCz were recorded to localize the HOMO and LUMO ( FIG. 4A ). The electrochemical data are illustrated in Table 1. Compared to the electron donor PTB7-Th, the HOMO and LUMO of MCz are at lower energy levels than those of conjugated polymers, making these materials sufficient for downhill electron transfer in bulk heterojunction organic solar cells ( FIG. 4B ). In one embodiment of the present disclosure, the materials were selected in part to cover a wide range of indoor LED emission spectra. [Table 1]

[0082] The absorption spectrum of MCz exhibits two main regions, 250–400 and 400–600 nm, respectively (Figure 5). The frontier molecular orbitals (HOMO and LUMO orbitals) of MCz are illustrated in Figure 6. The LUMO and LUMO+1 exhibit atomic contributions located primarily on the π system of the 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile moiety (i.e., the electron-withdrawing moiety), while the HOMO and HOMO-1 atomic contributions are mostly located on the π system of the carbazole moiety (i.e., the electron-donating moiety) (Table 2). Electronic transitions between these HOMO and LUMO molecular orbitals result in charge-transfer excited states, i.e., N-alkylcarbazole → malononitrile moieties, demonstrating the push-pull characteristics of MCz. [Table 2]

[0083] TDDFT calculates that the lowest energy spin-allowed transition is located at 523 nm (Table 3). This value compares favorably with the experimental band maximum at 520 nm (Figure 5, top). This transition consists of 98% of the HOMO → LUMO transition, and the calculated oscillator strength (f) is large, which explains the observed large absorption (ε = 46700 M -1 cm -1 ) is consistent with the charge transfer (CT) assignment. This transition is well isolated from the next two transitions at 455 and 438 nm, respectively, and is composed of the HOMO → LUMO +1 and HOMO -1 → LUMO transitions in different proportions. These latter two electronic transitions also lead to a charge-excited state, i.e., the N-alkylcarbazole → malononitrile moiety. Finally, the first electronic transition of 100 was calculated to generate a simulated spectrum (Figure 7). The simulated spectrum is similar to that of the experimental spectrum (Figure 5), confirming that the computational method is sufficient to explain the push-pull ability of MCz, thus supporting the charge transfer (CT) assignment. [Table 3]

[0084] MCz emits strongly both in solution and in the solid state (Figure 5). The fluorescence lifetime (τ F ) data are illustrated in Table 4. The nanosecond (ns) time scale is consistent with emission arising from the singlet state (i.e., fluorescence). For the sample at 298 K, a multi-exponential decay is observed (Figure 8). Speculatively, rotation about the C-C single bond between the carbazole moiety (i.e., electron-donating moiety (D)) and the malononitrile moiety (i.e., electron-withdrawing moiety (A)) could generate multiple conformers. The drop in thermal energy at 77 K could favor the lowest energy conformation. For CHCl at 298 K, τ F is less than 0.10 ns (i.e., the measurement limit, the full width at half maximum (FWHM) of the excitation pulse is about 100 ps). A very weak fluorescence signal can be observed in CH2Cl2 at 298 K, which can be easily explained by the quenching effect of this solvent. F (less than 0.10 ns) is accompanied by lower fluorescence intensity. Chlorinated solvents such as CHCl3 and CH2Cl2 are known to often quench fluorescence. Both results show quenching, which is consistent with the known ability of carbazole to photooxidize in the presence of halocarbons. [Table 4]

[0085] Devices were prepared containing binary compositions including an electron acceptor material A1 (MCz or MCzM) and an electron donor material D1 (PTB7-Th; HOMO = -5.26 eV and LUMO = 3.62 eV). The optical spectra extended up to 780 nm. Photovoltaic metrics are illustrated in Tables 5 and 6. [Table 5]

[0086] The active layer based on the binary composition (MCz:PTB7-Th) achieved a maximum PCE of 9.43% with the following photovoltaic parameters: sc=18.26mA / cm 2 , V oc = 0.82 V, FF = 0.63. These results compare favorably with the MCzM:PTB7-Th binary composition. Interestingly, the transition from the MCzM:PTB7-Th binary composition to the MCz:PTB7-Th binary composition showed little loss in device performance (PDE of 11.72% vs. 9.43%). [Table 6]

[0087] The active layer based on the binary composition (MCz:PTB7-Th) achieved a maximum PCE of 16.86% with the following photovoltaic parameters: sc =91.85mA / cm 2 , V oc = 0.74 V, FF = 0.62. These results compare favorably with the MCzM:PTB7-Th binary composition. Interestingly, the transition from the MCzM:PTB7-Th binary composition to the MCz:PTB7-Th binary composition again showed little loss in device performance (PDE of 16.86% vs. 18.55%).

[0088] The synthesis of MDCzM-4F and MDCzM-4H according to one embodiment of the present disclosure is illustrated in Scheme 2. [ka]

[0089] In one aspect, the present disclosure provides a binary composition comprising an electron acceptor material A1 and an electron donor material D1, wherein the electron acceptor material A1 is of formula Ib: [ka] wherein R1 and R2 are each independently a linear or branched C 6-15-alkyl; X1, X2, X3, and X4 are each independently H, F, Cl, or Br; and T1 and T2 are each independently =O, =C(CN)2, or =CHCN.

[0090] In one embodiment of the present disclosure, the binary composition comprises a MDCzM-4F:P3HT system. In one embodiment of the present disclosure, the binary composition comprises a MDCzM-4H:P3HT system. In one embodiment of the present disclosure, the electron acceptor material A1 has any of the following structures: [ka] ,

[0091] Photophysical data for both P3HT and MDCzM-4F were obtained and are illustrated in Table 7 and Figures 10A and 11A. [Table 7]

[0092] Photophysical data for both P3HT and MDCzM-4H were obtained and are illustrated in Table 8 and Figures 10B and 11B. [Table 8]

[0093] experiment Several non-limiting examples illustrating the preparation of novel carbazole-based non-fullerene, binary and ternary compositions, and devices containing them, according to various embodiments of the present disclosure are provided in the following sections. The following non-limiting examples are illustrative of the present disclosure.

[0094] material PTB7-Th (poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl})) was purchased from Odessa and used as received. MCzM was synthesized according to literature procedures.

[21]

[0095] Preparation of MCz 2-(3-Oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (575 mg, 2.96 mmol) and 9-(2-ethylhexyl)-9H-carbazole-3-carbaldehyde (492 mg, 1.6 mmol) were dissolved in dichloroethane (50 mL) and pyridine (1.3 mL) under stirring. The mixture was then refluxed for 1 h. After cooling to room temperature, the crude material was purified by column chromatography on silica gel with EtOAc / hexane (1:3 to 1:4) as the mobile phase to give 290 mg (37.5%) of a dark red solid. 1 H NMR(400 MHz,CDCl3)δ 9.21(s,1H aro ), 8.77(s,1H aro ), 8.67-8.65(d,1H aro ), 8.47-8.45(d,1H aro ), 8.21-8.19(d,1H aro ), 7.94-7.92(m,1H aro ), 7.76-7.72(m,2H aro ), 7.54-7.50(t,1H aro ), 7.42-7.40(d,2H aro ), 7.36-7.32(t,1H aro ),4.17-4.15(m,CH2),2.08-2.02(quint,CH),1.44-1.22(m,4CH2),0.94-0.91(t,CH3),0.88-0.85(t,CH3). 13C NMR(101 MHz,CDCl3)δ 187.14,163.09,149.64,144.76,141.71,139.72,137.50,135.07,134.56,134.06, 129.55,127.04,125.65,125.15,124.51,124.03,123.76,123.29,121.18,121.10,1 Crystals of MCz for use in X-ray diffraction were obtained by dissolving the powder in a hot mixture of acetonitrile / toluene (1:1). Slow evaporation over 3 days yielded purple needles of the appropriate size suitable for X-ray diffraction.

[0096] Preparation of MDCzM-4F and MDCzM-4F (Scheme 2) 9,9'-bis(2-ethylhexyl)-9H,9'H-3,3'-bicarbazole(3) Trifluoroacetic acid (10 equivalents) was used to prepare compound 3. The crude material (obtained as a mixture, 85-90% of the desired product 3) was used directly in the next step.

[0097] 9,9'-Bis(2-ethylhexyl)-9H,9'H-[3,3'-bicarbazole]-6,6'-dicarbaldehyde (4) POCl3 (8.4 ml, 25 equiv.) was carefully added to a mixture of 3 (2 g, 3.6 mmol) in DMF (7 ml, 25 equiv.) with stirring under Ar at room temperature. The reaction mixture was stirred at 100 °C for 2 h in a sealed Schlenk tube. TLC revealed a large amount of starting material and a monoaldehyde. Additional DMF (7 ml, 25 equiv.) was added, and the reaction was continued overnight. After cooling to room temperature, the resulting reaction cake was dissolved in 250 ml of DCM, carefully mixed with solid Na2CO3, and stirred for 5 h. The product was extracted with DCM (2 × 250 ml), and the organic layers were combined, washed with water and brine, dried over Na2SO4, filtered, and concentrated. The crude product was adsorbed onto silica and chromatographed (SiO2 column) using DCM as the eluent to give 1.4 g of pure product (Y = 64%). 1 H-NMR (400 MHz, CDCl3): δ 10.15(s,2H),8.72(d,J=1.29 Hz,2H),8.50(d,J=1.54 Hz,2H),8.06(dd,J1=8.56 Hz,J2=1.50 Hz,2H),7.92(dd,J1=8.49 Hz,J2=1.74 Hz,2H),7.57(d,J=8.58 Hz,2H),7.51(d,J=8.57,2H),4.18-4.27(m,4H),2.15(hep,J=5.86 Hz,2H),1.51-1.28(m,16H),0.99(t,J=7.41 Hz,6H),0.91(t,J=7.12 Hz,6H). 13 C-NMR (400 MHz, CDCl3):δ 191.73,144,98,140.84,134.21,128.59,127.15,126.39,124.18,123.66,123.19 ,119.21,110.09,109.45,47.88,39.49,31.01,28.79,24.42,23.06,14.06,10.94.

[0098] 2,2'-((2Z,2'Z)-((9,9'-bis(2-ethylhexyl)-9H,9'H-[3,3'-bicarbazole]-6,6'-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))-imalononitrile, MDCzM (5). In a sealed Schlenk tube, a mixture of compound 4 (300 mg, 0.49 mmol), 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)-malononitrile (285 mg, 3 equivalents), and pyridine (3 ml) in toluene (45 ml) was stirred at 150 °C under Ar for 40 min. The reaction mixture was then cooled to room temperature and concentrated. The crude material was triturated in EtOH and filtered. The resulting material was suspended in a large amount of CHCl3 and filtered. The filtrate was evaporated and purified in three portions by preparative TLC using DCM / Hex=9 / 1 as the eluent to give 130 mg of a deep purple product. R f =0.94(DCM)(Y=28%). 1 H-NMR (400 MHz, CDCl3): δ 9.38(s,2H),8.74(s,2H),8.49(d,J=7.70 Hz,2H),8.41(dd,J1=8.86 Hz,J2=1.71 Hz,2H),8.38(d,J=1.76 Hz,2H),8.01(dd,J1=7.15 Hz,J2=1.48 Hz,2H),7.87(dd,J1=8.48 Hz,J2=1.81 Hz,2H),7.65(ddd,J1=7.41 Hz,J2=7.33 Hz,J3=1.09 Hz,2H),7.60(ddd,J1=7.51 Hz,J2=7.38 Hz,J3=1.45 Hz,2H),7.49(d,J=8.51 Hz,2H),7.44(d,J=8.81 Hz,2H),4.28-4.16(m,4H),2.17-2.06(m,2H),1.50-1.30(m,16H),0.99(t,J=7.38 Hz,6H),0.92(t,J=7.07 Hz,6H). 13C-NMR (100 MHz, CDCl3):δ 187.12,162.59,149.05,144.86,140.74,139.42,137.33,134.74,134.41,134.36,134.30,129.44,126.47,125.47,124.75,124.60 ,124.01,123.83,123.81,119.54,114.88,114.67,110.18,109.42,69.36,47.90,39.54,31.03,28.83,24.45,23.05,14.07,10.91.

[0099] 2,2'-((2Z,2'Z)-((9,9'-bis(2-ethylhexyl)-9H,9'H-[3,3'-bicarbazole]-6,6'-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimaronitrile, MDCzM-4F(6). In a sealed Schlenk tube, a mixture of compound 4 (100 mg, 0.17 mmol), 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)-malononitrile (150 mg, 4 equiv.), and pyridine (1 ml) in toluene (8 ml) was stirred at 150 °C under Ar for 2 h. The reaction mixture was then cooled to room temperature and concentrated. The crude material was triturated in EtOH and filtered. The resulting black material was suspended in a large amount of CHCl and filtered. The filtrate was adsorbed onto SiO and subjected to chromatography (SiO column) using DCM as the eluent. The product (51 mg) was then recrystallized from a CHCl / Hex mixture to give 31 mg of a dark purple solid. f =0.84(DCM);Y=9%. 1H-NMR (400 MHz, CDCl3): δ 9.63(s,2H),8.64(s,2H),8.29(s,2H),8.17(d,J=8.67 Hz,2H),8.11-8.04(m,2H),7.88(dd,J1=J2=7.64 Hz,2H),7.82(d,J=8.46 Hz),7.51(d,J=8.42 Hz,4H),4.35-4.26(m,4H),2.20-2.12(m,2H),1.50-1.32(m,16H),1.02(t,J=7.35 Hz,6H),0.94(t,J=7.04,6H). 19 F-NMR(400 MHz, CDCl3):δ -123.24,-123.50. 13 C-NMR (100 MHz, CDCl3): δ 184.91,159.59,155.39(m),152.94(m),148.52,145.04,140.91,135.76(dd,J1=7.61 Hz,J2=4.04 Hz),135.33,134.93(dd,J1=4 Hz,J2=3 Hz),134.51,128.67,126.47,124.52,124.36,124.10,123.77,119.10,114.42,114.05,113.84(d,J=21.06 Hz),112.88(d,J=18.50),110.36,109.87,48.13,39.64,31.09,29.66,28.79,24.50,22.94,13.87,10.77.

[0100] Thin films of P3HT and MDCzM-4H were prepared on thin quartz plates by depositing 50 μl of a 10 mg / mL solution while spinning at 3000 rpm for 30 seconds. Films of P3HT:MDCzM-4H (1:1) were obtained by subjecting the quartz plates to the same conditions using the same total concentration of the 1:1 solution. All thin films were used as is without further treatment.

[0101] Thin films of P3HT and MDCzM-4F were prepared on thin quartz plates by depositing 50 μl of a 10 mg / mL solution while spinning at 3000 rpm for 30 seconds. Films of P3HT:MDCzM-4F (1:1) were obtained by subjecting the quartz plates to the same conditions using the same total concentration of the 1:1 solution. All thin films were used as is without further treatment.

[0102] equipment Solid-state UV-vis spectra were recorded at 298 K and 77 K on a Varian Cary 50 spectrophotometer using a high-angle transmission device and a 77 K sample holder designed in-house. Steady-state emission and excitation spectra were measured on an Edinburgh Instruments FLS980 Phosphorimeter equipped with a single monochromator. Steady-state emission spectra were recorded using capillary tubes for the solid state, NMR tubes for the 77 K measurements, and airtight 1 cm cuvettes for the 298 K solution measurements, all prepared in a glovebox. These spectra were corrected for instrument response. Phosphorescence lifetime measurements were performed using an Edinburgh Instruments FLS980 Phosphorimeter equipped with a "flash" pulse lamp. The pulse frequency was adjusted from 1 Hz to 100 Hz. For comparison purposes, all lifetime values ​​from deconvolution and distribution lifetime analysis, as well as multiexponential analysis, were obtained. Photoluminescence quantum yields were obtained on a HORIBA FluoroF spectrophotometer equipped with an integrating sphere. The slit was kept constant to obtain a Rayleigh scattering intensity of 1,000,000 Ct at 500 nm.

[0103] electrochemistry Ag / Ag + Cyclic voltammetry measurements of MCz were carried out using a saturated KCl reference electrode, a Pt mesh as the counter electrode, and a Pt disk electrode as the working electrode. The ferrocene / ferrocene couple was used as the internal reference. CV measurements were carried out in distilled dichloromethane. Argon-degassed 10% tetra-butylammonium hexafluorophosphate was used. -1All measurements were performed using M solution. All CVS measurements were performed using 10 M solution in dichloromethane. -5 It was started from a solution of M.

[0104] Single crystal X-ray diffraction C 33 H 29 Purple needle-like specimens of NO(MCz) were mounted on a Bruker APEX-II DUO equipped with a nitrogen jet stream cryogenic system (Oxford Cryosystems). The X-ray source was either graphite monochromated Mo-Kα radiation (λ = 0.71073 Å) from a sealed tube or a Cu (λ = 1.54186 Å) microfocus tube I μS with MX optics from Incoatec. Lattice parameters were obtained by the least-squares method to determine the best fit to an optimized set of angles for the entire set of collected reflections. Intensity data were recorded as φ and ω scans. Data were reduced using SAINT v8.37A (Bruker, 2015) software, and absorption correction was performed using SADABS-2016 / 2 (Bruker, 2016). Structures were solved using the Bruker SHELXTL Software Package. Refinement was performed on the complete set of reflections using shelxl-crystal structure refinement-multi-cpu version, George M. Sheldrick 1993-2018 version 2018 / 3. All non-hydrogen atoms were refined with anisotropic thermal parameters.

[0105] Density functional theory calculations Density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations were performed on the Mammoth supercomputer supported by Calcul Quebec using Gaussian 16 at the Universite de Sherbrooke. The crystallographic information file (CIF) from the X-ray crystal structure of MCz was used as the starting point for the calculations. DFT (ground state) and TDDFT calculations were performed using the B3LYP method. The 6-31g(d,p) basis set was used for all atoms. All calculations were performed using the dichloromethane CPCM solvent field. No imaginary frequency solutions were observed, verifying correct energy minimization after optimization. GaussSum 3.0 was used to obtain the calculated absorption spectra. Isodensity surfaces were generated using a contour value of 0.0432, with red lobes being positive and blue lobes being negative.

[0106] Although the present disclosure has been described with reference to particular examples, it is to be understood that the present disclosure is not limited to the disclosed examples. On the contrary, the present disclosure is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

[0107] All publications, patents, and patent applications cited in this disclosure are herein incorporated by reference in their entirety to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference in its entirety.

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Claims

1. A compound of formula Ia, 【Chemistry 1】 During the ceremony, R is a linear or branched C6-10-alkyl group. X １ , X ２ , X ３ , and X ４ However, each is independently H, F, Cl, or Br. T １ and T ２ However, each is independent of the other, =O, =C(CN) ２ , or =CHCN, provided that T1 and T2 are not simultaneously =O. compound.

2. Including the structure of formula IIa or formula IIIa, 【Chemistry 2】 During the ceremony, R is a linear or branched C6-10-alkyl group. X １ , X ２ , X ３ , and X ４ are each independently H, F, Cl or Br, the compound according to claim 1.

3. X １ , X ２ , X ３ , and X ４ The compound according to claim 1, wherein each is independently H and / or R is 2-ethylhexyl.

4. A compound of formula Ib, 【Transformation 3】 During the ceremony, R １ and R ２ However, each independently forms a linear or branched chain C ６－１５ -It is alkyl, X １ , X ２ , X ３ , and X ４ However, each is independently H, F, Cl, or Br. T １ and T ２ However, each is independent of the other, =O, =C(CN) ２ A compound that is either , or =CHCN.

5. Electron acceptor material A １ And, electron donor material D １ A composition comprising the electron acceptor material A １ However, this is the one in equation Ia, 【Chemistry 4】 During the ceremony, R is a linear or branched C6-10-alkyl group. X １ , X ２ , X ３ , and X ４ However, each is independently H, F, Cl, or Br. T １ and T ２ However, each is independent of the other, =O, =C(CN) ２ A composition in which T1 and T2 are not simultaneously equal to O, or = CHCN.

6. The aforementioned electron acceptor material A １ However, it has the structure of formula IIa or IIIa, 【Transformation 5】 During the ceremony, R is a linear or branched C6-10-alkyl group. X １ , X ２ , X ３ , and X ４ The composition according to claim 5, wherein each is independently H, F, Cl, or Br.

7. X １ , X ２ , X ３ , and X ４ The composition according to claim 5, wherein each is independently H and / or R is 2-ethylhexyl.

8. The aforementioned electron donor material D １ The composition according to claim 5, wherein the composition comprises a p-type organic semiconductor material.

9. The aforementioned electron donor material D １ However, (Poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl}))(PTB7-Th),Poly(3-hexylthiophene)(P3HT),Poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5 The composition according to claim 5, comprising ,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole) (PPDT2FBT), or poly[9-(1-octylnonyl)-9H-carbazole-2,7-diyl]-2,5-thiophendiyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophendiyl] (PCDTBT).

10. The composition according to claim 5, wherein the composition comprises a mass ratio (w / w) of receptor material to donor material in the range of about 0.5:1.0 to about 1.0:0.

5.

11. The composition according to claim 5, wherein the composition is slot die coated or spin coated.

12. At least two electron acceptor materials A １ and A ２ And at least electron donor material D １ A composition comprising the electron acceptor material A １ and A ２ However, this is the one in equation Ia, 【Transformation 6】 During the ceremony, R is a linear or branched C6-10-alkyl group. X １ , X ２ , X ３ , and X ４ However, each is independently H, F, Cl, or Br. T １ and T ２ However, each is independent of the other, =O, =C(CN) ２ A composition in which T1 and T2 are not simultaneously equal to O, or = CHCN.

13. The two electron acceptor materials A mentioned above １ and A ２ At least one of them has the structure of formula IIa or IIIa, 【Transformation 7】 During the ceremony, R is a linear or branched C6-10-alkyl group. X １ , X ２ , X ３ , and X ４ The composition according to claim 12, wherein each of them is independently H, F, Cl, or Br.

14. X １ , X ２ , X ３ , and X ４ The composition according to claim 12, wherein each is independently H and / or R is 2-ethylhexyl.

15. The aforementioned electron donor material D １ The composition according to claim 12, wherein the composition comprises a p-type organic semiconductor material.

16. The aforementioned electron donor material D １ However, (Poly([2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl}))(PTB7-Th),Poly(3-hexylthiophene)(P3HT),Poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5 The composition according to claim 12, comprising ,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole) (PPDT2FBT), or poly[9-(1-octylnonyl)-9H-carbazole-2,7-diyl]-2,5-thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl] (PCDTBT).

17. The composition according to claim 12, wherein the composition comprises a mass ratio (w / w) of receptor material to donor material in the range of about 0.5:1.0 to about 1.0:0.

5.

18. The composition according to claim 12, wherein the composition is slot die coated or spin coated.

19. At least two electron acceptor materials A １ and A ２ And at least electron donor material D １ A composition comprising the electron acceptor material A １ and A ２ However, these are equations Ia and Ib, 【Transformation 8】 During the ceremony, R, R １ , and R ２ However, each independently forms a linear or branched chain C ６－１５ -It is alkyl, X １ , X ２ , X ３ , and X ４ However, each is independently H, F, Cl, or Br. T １ and T ２ However, each is independent of the other, =O, =C(CN) ２ A composition that is, or =CHCN.

20. Organic solar cells, anode and cathode, A photoactive layer between the anode and the cathode, An organic solar cell in which the photoactive layer comprises an electron donor / acceptor material, wherein the electron acceptor material is as defined in claim 1.

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