Azaacenes Based Electroactive Materials: Preparation, Structure, Electrochemistry, Spectroscopy and Applications—A Critical Review †
Abstract
:1. Acenes vs. Azaacenes—Generalities
2. Synthesis of Azaacenes
3. Spectroscopic and Electrochemical Properties of Linear Azaacenes
4. Supramolecular Organization of Linear Azaacenes
5. Degradation of Linear Azaacenes
6. Azaacenes Containing Pyrene-Type Units
7. Spatially Extended Azaacenes
8. Nonlinear Azaacenes
9. Applications of Azaacenes
10. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Compound | E1/2red # vs. Fc/Fc+ [V] | EA * [eV] | Eg opt [eV] |
---|---|---|---|
Acenes | |||
Naphthalene | −3.44 [13] | 0.77 | 4.14 [14] |
Anthracene | −2.91 [13] | 1.40 | 3.20 [14] |
Azaacenes | |||
Quinoline (1N) | −2.77 [15] | 1.56 | 3.94 [16] ** |
Quinoxaline (2N) | −2.26 [15] | 2.16 | 3.85 [17] ** |
Acridine (1N) | −2.26 [15] | 2.16 | 3.22 [18] ** |
Phenazine (2N) | −1.83 [15] | 2.67 | 3.07 [19] ** |
Pyrazinoquinoxaline (4N) | −1.60 [20] | 2.94 | 2.95 [21] ** |
Compounds | E1/2red vs. Fc/Fc+ [V] | EA * [eV] | Eg opt [eV] |
---|---|---|---|
1a | −1.1 | 3.53 | 2.38 |
1b | −0.8 | 3.89 | 1.84 |
1c | −0,7 | 4.00 | 1.49 |
2a | −1.1 | 3.53 | 2.20 |
2b | −0.8 | 3.89 | 1.69 |
2c | −0.48 | 4.26 | 1.35 |
Compound | λmax abs [nm] | λmax emi [nm] | Stokes Shift [nm] |
---|---|---|---|
3a | 572 | 577 | 5 |
3b | 602 | 616 | 14 |
3c | 620 | 627 | 7 |
4a | 548 | ||
4b | 574 | ||
4c | 598 | ||
5a | 586 | 590 | 4 |
5b | 602 | 643 | 44 |
5c | 611 | 657 | 42 |
Compound | Eg opt [nm]/[eV] | Ered vs. Fc/Fc+ [V] | EA * [eV] |
---|---|---|---|
6a | 737/1.68 | −0.60 | 4.12 |
6b | 752/1.65 | −0.60 | 4.12 |
6c | 744/1.67 | −0.70 | 4.00 |
7a | 862/1.44 | −0.55 | 4.18 |
7b | 1039/1.19 | −0.48 | 4.26 |
7c | 1000/1.24 | −0.53 | 4.20 |
8a | 780/1.59 ** | −0.52 | 4.22 |
8b | 867/1.43 ** | −0.27 | 4.51 |
Compounds | λmax abs [nm] | Eg opt [eV] | Eox1 [V] | Eox2 [V] |
---|---|---|---|---|
9a | 413 | 2.60 | 0.26 | 0.48 |
9b | 493 | 2.17 | 0.24 | 0.42 |
9c | 455 | 2.36 | 0.25 | 0.44 |
9d | 560 | 1.88 | 0.22 | 0.37 |
Compounds | λmax abs [nm] | Eg opt [eV] | Ered vs. Fc/Fc+ [V] | EA *** [eV] | Compounds | λmax abs [nm] | Eg opt [eV] | Ered vs. Fc/Fc+ [V] | EA *** [eV] |
---|---|---|---|---|---|---|---|---|---|
10 | 417 | 2.81 | −0.79 | 3.90 | 19 | 485 | 2.42 | −1.51 * | 3.05 |
11 | 435 | 2.76 | −0.76 | 3.93 | 20 | 441 | 2.51 | −1.69 ** | 2.84 |
12 | 440 | 2.70 | −0.73 | 3.97 | 21 | 471 | 2.37 | −1.54 ** | 3.01 |
13 | 482 | 2.37 | −0.21 | 4.58 | 22 | 464 | 2.41 | −1.62 ** | 2.92 |
14 | 455 | 2.09 | −1.42 * | 3.15 | 23a | 443 | 2.65 | −1.68 ** | 2.85 |
15 | 571 | 1.85 | −0.71 * | 3.99 | 23b | 500 | 2.34 | −1.22 ** | 3.39 |
16 | 421 | 2.88 | −1.73 * | 2.79 | 23c | 525 | 2.25 | −1.19 ** | 3.43 |
17 | 436 | 2.69 | −1.57 * | 2.98 | 23d | 529 | 2.22 | −1.16 ** | 3.46 |
18 | 425 | 2.78 | −1.44 * | 3.13 | 23e | 538 | 2.18 | −1.14 ** | 3.48 |
Compounds | λmax abs [nm] | λmax emi [nm] | Eg opt [eV] | Ered vs. Fc/Fc+ [V] | EA * [eV] |
---|---|---|---|---|---|
24a | 471 | 552 | 2.43 | −1.01 | 3.64 |
24b | 508 | 593 | 2.23 | −0.71 | 3.99 |
24c | 530 | 605 | 2.13 | −0.60 | 4.12 |
24d | 543 | 615 | 2.08 | −0.53 | 4.20 |
25 | 399 | 504 | 2.95 | −0.91 | 3.90 |
Compounds | λmax abs [nm] | λmax emi [nm] | Eg opt [eV] | Ered vs. Fc/Fc+ [V] | EA * [eV] |
---|---|---|---|---|---|
26a | 378 | 422 | 2.99 | −1.50 | 3.90 |
26b | 497 | 508 | 2.42 | −1.63 | 3.06 |
26c | 597 | 604 | 1.98 | −1.50 | 2.91 |
26d | 595 | 607 | 2.01 | −1.09 | 3.06 |
27a | 369 | 427 | 3.06 | −1.85 | 3.54 |
27b | 485 | 497 | 2.47 | −1.56 | 2.65 |
27c | 582 | 590 | 2.07 | −1.40 | 2.99 |
27d | 586 | 599 | 2.05 | −1.03 | 3.18 |
Compounds | λmax abs [nm] | λmax emi [nm] | Eg opt [nm]/[eV] | Ered vs. Fc/Fc+ [V] | EA * [eV] |
---|---|---|---|---|---|
28a | 391 | 413 | 409/3.03 | −1.58 | 2.97 |
28b | 490 | 500 | 504/2.46 | −1.55 | 3.00 |
28c | 589 | 594 | 603/2.06 | −1.33 | 3.26 |
29a | 388 | 433 | 411/3.02 | −1.82 | 2.68 |
29b | 493 | 506 | 510/2.43 | −1.57 | 2.98 |
29c | 596 | 601 | 610/2.03 | −1.34 | 3.25 |
Compound | λmax abs [nm] | λmax emi [nm] | Eg opt [nm]/[eV] | Ered vs. Fc/Fc+ [V] | EA * [eV] |
---|---|---|---|---|---|
30 | 570 | 577 | 585/2.12 | −1.23 ** | 3.38 |
31 | 693 | 699 | 709/1.75 | −1.05 ** | 3.59 |
32 | 544 | 553 | 558/2.22 | −1.79 ** | 2.72 |
33 | 681 | 694 | −/1.94 | −0.68 | 4.03 |
34 | 653 | 699 | −/1.75 | −0.76 | 3.93 |
35 | 712 | 688 | −/1.75 | −0.51 | 4.23 |
Compounds | λmax abs. [nm] | λmax emi [nm] | Eg opt [eV] | Ered vs. Fc/Fc+ [V] | EA [eV] |
---|---|---|---|---|---|
36 | 499 | 501 | - | −1.20 | 3.41 |
37 | 493 | 515 | 2.40 | −1.63 | 2.91 |
38 | 554 | - | 2.23 | - | - |
39 | 515 | 524 | 2.33 | −1.62 | 2.92 |
40 | 369 | 370 | 4.11 | −2.02 | 2.45 |
41 | 423 | 431 | 3.18 | −1.77 | 2.74 |
42 | 416 | 425 | - | −1.88 | 2.61 |
Compound | Device’s Properties |
---|---|
Emitters in organic light emitting diode | |
43 | maximum luminance 1000 cd m−2 * efficiency 5 cd A−1 EQE = 0.53%, λmax emi = 540 nm * [93] |
44 | maximum luminance 2321 cd m−2 efficiency 0.79 cd A−1, λmax emi = 547 nm [85] |
45 | maximum luminance 5792 cd m−2 * efficiency 2.88 cd A−1 λmax emi = 502 nm [113] |
46 | maximum luminance > 600 cd m−2 * efficiency 5.4 cd A−1 EQE = 7.2%, λmax emi = 640 nm [98] |
47 | maximum luminance > 300 cd m−2 * efficiency 0.8 cd A−1 EQE = 2.0%, λmax emi = 665 nm [98] |
48 | maximum luminance > 300 cd m−2 * EQE = 22.80%, λmax emi = 698 nm [114] |
49 | maximum luminance > 10,000 cd m−2 EQE = 26.00%, [115] |
50 | efficiency 51.8 cd A−1 EQE = 21.8%, λmax emi = 577 nm [116] |
51 | efficiency 47.1 cd A−1 EQE = 23.8%, λmax emi = 587 nm [116] |
52 | maximum luminance > 6000 cd m−2 * EQE = 19.4%, λmax emi = 580nm [97] |
53 | maximum luminance > 10,000 cd m−2 * EQE = 22.1%, λmax emi = 547 nm [97] |
54 | maximum luminance > 1000 cd m−2 * EQE = 3.3%, λmax emi = 536 nm phosphorescence [33] |
55 | maximum luminance 8600 cd m−2, EQE = 0.33%, λmax emi = 511 nm [117] |
56 | maximum luminance > 200 cd m−2, efficiency 1 cd A−1, λmax emi = 590 nm [70] |
57 | maximum luminance 593 cd m−2 *, efficiency 0.85 cd A−1, λmax emi = 502 nm [118] |
58 | maximum luminance 20780 cd m−2, EQE = 3.1%, λmax emi = 500 nm [119] |
59 | maximum luminance > 500 cd m−2 *, efficiency 11.6 cd A−1, EQE = 10.4%, λmax emi = 456 nm [120] |
60 | maximum luminance 920 cd m−2 *, efficiency 80 cd A−1, EQR = 0.53%, λmax emi = 495 nm [31] |
61 | maximum luminance 595 cd m−2 *, efficiency 7.0 cd A−1, EQE = 2.0%, λmax emi = 520 nm* [15] |
62 | maximum luminance 80 cd m−2, λmax emi = 508 nm [89] |
63 | efficiency 2.13 cd A−1, EQE = 4.61%, λmax emi = 440 nm [121] |
64 | EQE = 0.05%, λmax emi = 970 nm [122] |
Acceptors for solar cells | |
65 | VOC = 0.81 V, FF = 37.3%, JSC = −6,77 mA cm2 PCE = 2.03% [101] |
66 | VOC = 0.75 V, FF = 38.3%, JSC = −5.66 mA cm2, PCE = 1.62% [35] |
67 | VOC = 0.80 V, FF = 41%, JSC = −6,6 mA cm2, PCE = 2.19% [37] |
68 | VOC = 0.85 V, FF = 36%, JSC = −7.51 mA cm2, PCE = 2.28% [36] |
Electron Transporting Layers for Perovskite Solar Cells | |
69 | μe = 2.8 × 10−4 cm2 V−1 s−1, μe = 2.7 × 10−3 cm2 V−1 s−1 (100 °C) [104] |
70 | μe = 4.7 × 10−4 cm2 V−1 s−1 [105] |
71 | μe = 1.73 × 10−2 cm2 V−1 s−1 [106] |
72 | μe = 1.9 × 10−4 cm2 V−1 s−1 [123] |
73 | μe = 5.13 × 10−3 cm2 V−1 s−1 [124] |
74 | μe = 1.68 × 10−3 cm2 V−1 s−1 (doped by Et3N) [125] |
Active layers in organic field effect transistors | |
75 | μe = 7 × 10−3 cm2 V−1 s−1 [69] |
76 | μe = 7 × 10−2 cm2 V−1 s−1 [126] |
77 | μe = 9 × 10−4 cm2 V−1 s−1 [127] |
78 | μe = 0.14 cm2 V−1 s−1, μh = 0.12 cm2 V−1 s−1 [109] |
79 | μe = 0.15 cm2 V−1 s−1, μh = 0.11 cm2 V−1 s−1 [108] |
80 | μe = 0.05 cm2 V−1 s−1, μh = 4 × 10−4 cm2 V−1 s−1 [107] |
81 | μe = from 1 do 3.3 cm2 V−1 s−1 (depend of temperatures of substrate—from 25 °C to 100 °C) [107]μe = 11 cm2 V−1 s−1 (measured in vacuum) [128] |
82 | μe = 3.5 × 10−4 cm2 V−1 s−1 [129] |
83 | μe = 27.8 cm2 V−1 s−1 (measured in vacuum) [111] |
84 | μe = 0.56 cm2 V−1 s−1 [130] |
85 | μe = 3.7 × 10−2 cm2 V−1 s−1 [131] |
86 | μh = 0.06 cm2 V−1 s−1 [110] |
87 | μh = 8.1 × 10−3 cm2 V−1 s−1 [132] |
88 | μe = 8.1 × 10−4 cm2 V−1 s−1, μh = 2 × 10−4 cm2 V−1 s−1 [133] |
Self-assembled monolayers (SAM) for functionalization of gold electrodes for organic field effect transistors | |
89 | on/off ratio increased from 102 to 104, μe = from 10−3 cm2 V−1 s−1 to 10−2 cm2 V−1 s−1 [134] |
Photocatode | |
90 | current density 0.13 mA cm−2 at −0.13 V (Evs RHE) [135] |
91 | Detected [112] |
Memory device | |
92 | “ON” state a 2.25 V, “OFF” state −0.95 V, 14 cycles of working [136] |
93 | “ON” state a ~3.00 V, “OFF” state −1.65 V *, [137] |
94 | “ON” state a ~2.2 V, “OFF” state −1.2 V * [138] |
95 | “ON” state a ~1.8 V, “OFF” state −2.0 V * [139] |
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Kotwica, K.; Wielgus, I.; Proń, A. Azaacenes Based Electroactive Materials: Preparation, Structure, Electrochemistry, Spectroscopy and Applications—A Critical Review. Materials 2021, 14, 5155. https://doi.org/10.3390/ma14185155
Kotwica K, Wielgus I, Proń A. Azaacenes Based Electroactive Materials: Preparation, Structure, Electrochemistry, Spectroscopy and Applications—A Critical Review. Materials. 2021; 14(18):5155. https://doi.org/10.3390/ma14185155
Chicago/Turabian StyleKotwica, Kamil, Ireneusz Wielgus, and Adam Proń. 2021. "Azaacenes Based Electroactive Materials: Preparation, Structure, Electrochemistry, Spectroscopy and Applications—A Critical Review" Materials 14, no. 18: 5155. https://doi.org/10.3390/ma14185155