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5,5′-Bis[9-(2-ethylhexyl)-9H-carbazol-3-yl]-4,4′-diphenyl-2,2′-bithiazole

1
Department of Life Sciences, School of Sciences, European University Cyprus, 6 Diogenis Str., Engomi, P.O. Box 22006, Nicosia 1516, Cyprus
2
Department of Chemistry, University of Cyprus, P.O. Box 20537, Nicosia 1678, Cyprus
*
Author to whom correspondence should be addressed.
Molbank 2024, 2024(1), M1761; https://doi.org/10.3390/M1761
Submission received: 14 December 2023 / Revised: 8 January 2024 / Accepted: 9 January 2024 / Published: 11 January 2024
(This article belongs to the Section Organic Synthesis)

Abstract

:
Stille coupling between 5,5′-dibromo-4,4′-diphenyl-2,2′-bithiazole and 9-(2-ethylhexyl)-3-(tributylstannyl)-9H-carbazole in the presence of Pd(Ph3P)2Cl2 in toluene, heated at reflux for 2 h, gave 5,5′-bis[9-(2-ethylhexyl)-9H-carbazol-3-yl]-4,4′-diphenyl-2,2′-bithiazole in 85% yield.

1. Introduction

Thiazoles (Figure 1) are well-studied heterocycles that are present in nature and show numerous applications in medicinal chemistry, already reviewed [1,2,3]. A well-known example of a natural thiazole is vitamin B1 (Thiamine) [4], while examples of thiazole-containing drugs are the antiviral ritonavir [5] and the H2-receptor antagonist famotidine [6]. Thiazole dimers are also important: 2,4′-bithiazoles appear in natural products such as the anticancer agents bleomycins [7], while 2,2′-bithiazoles have been studied as electron acceptors with potential applications in materials sciences [8,9].
Our pursuit of 2,2′-bithiazoles began in 2015 when we identified quinoidal 2,2′-bithiazole 1 as a side product during our investigation into the chemistry of 1,2,3-dithiazoles [10]. Subsequently, our group devised a high-yielding synthetic route towards (2E,5Z,5′Z)-5,5′-diarylimino quinoidal 2,2′-bithiazoles 2 (Figure 2) [11].
During the above studies, we had also embarked on preparing donor–acceptor–donor (D-A-D) molecules for solution-processed bulk heterojunction (BHJ) solar cells. In this regard, we investigated small molecules and polymers containing non-S-oxidized 4H-1,2,6-thiadiazin-4-ones, which we combined with PC70BM to yield BHJ solar cells with Power Conversion Efficiencies (PCEs) of ~3% for the former and up to 3.8% for the latter [12,13].
Interestingly, carbazole-bound 2,2′-bithienyls 3 [14,15,16,17] have been used in various optoelectronic applications, such as photoelectric conversion agents for imaging [14], organic field-effect transistors [15] and organic light-emitting diodes [16], and they have been combined to BODIPY units as potential hole transport materials for perovskite solar cells [17]. As such, to enhance the PCE of the solar cells under our investigation, we chose to explore the use of analogous 2,2′-bithiazole derivatives as non-fullerene acceptors. To the best of our knowledge, there are no reports of the use of 2,2′-bithiazole-carbazoles in OPV devices: a Reaxys search revealed only two analogous 2,2′-bithiazole-carbazoles 4 and 5 (Figure 3) that appear on PubChem (ID 102230564 and 122233114, respectively) without any reported experimental data.
Herein, we report the synthesis of a new 2,2′-bithiazole bearing carbazole substituents. As demonstrated in our previous study [12], these substituents were found to expand the π–π conjugation, thereby facilitating charge transfer.

2. Results and Discussion

The target, 5,5′-bis[9-(2-ethylhexyl)-9H-carbazol-3-yl]-4,4′-diphenyl-2,2′-bithiazole (6), was synthesized via our adapted Stille coupling protocol developed for halothiadiazines [12]. The starting material, bithiazole 7, was readily obtained in two steps with an overall yield of 58%, starting from 2-bromoacetophenone and rubeanic acid [11,18]. Additionally, the tributylstannyl reagent, 9-(2-ethylhexyl)-3-(tributylstannyl)-9H-carbazole (8), had been previously used effectively by us to prepare thiadiazine oligomers [12]. The Stille coupling proceeded smoothly to give the expected bithiazole 6 in 85% yield (Scheme 1).
The UV-vis spectrum of bithiazole 6 in DCM exhibited a lowest energy absorption band at λmax at 405 nm (log ε 3.30) with an onset value of 472 nm corresponding to an optical band gap (Egopt) of 2.63 eV (Table 1). The bithiazole was also analyzed using cyclic voltammetry (CV) that revealed one reversible reduction and one irreversible oxidation (see Supplementary Materials). The dimer 6 showed an electrochemical HOMO value of −5.84 eV, a LUMO value of −3.68 eV and an electrochemical band gap (Egechem) of 2.16 eV (Table 1). These values are close to the respective HOMO and LUMO values of PCBM, a commonly used fullerene acceptor molecule, of −6.2 eV and −3.95 eV [19].
Bithiazole 6 showed good optical absorption coverage with P3HT; however, initial OPV device studies using the title molecule in combination with P3HT in BHJ solar cells were unsuccessful owing to fabrication issues and were not pursued further. Potentially, bithiazole 6 could find similar optoelectronic D-A-D applications to the bithienyls mentioned above.

3. Materials and Methods

The reaction mixture was monitored by TLC using commercial glass-backed thin-layer chromatography (TLC) plates (Merck Kieselgel 60 F254). The plates were observed under UV light at 254 and 365 nm. The melting point was determined using a PolyTherm-A, Wagner & Munz, Kofler—Hotstage Microscope apparatus (Wagner & Munz, Munich, Germany). The solvent used for recrystallization is indicated after the melting point. The UV-vis spectrum was obtained using a Perkin-Elmer Lambda-25 UV/vis spectrophotometer (Perkin-Elmer, Waltham, MA, USA) and inflections are identified by the abbreviation “inf”. The IR spectrum was recorded on a Shimadzu FTIR-NIR Prestige-21 spectrometer (Shimadzu, Kyoto, Japan) with Pike Miracle Ge ATR accessory (Pike Miracle, Madison, WI, USA), and strong, medium and weak peaks are represented by s, m and w, respectively. 1H and 13C NMR spectra were recorded on a Bruker Avance 500 instrument (at 500 and 125 MHz, respectively (Bruker, Billerica, MA, USA)). Deuterated solvents were used for homonuclear lock and the signals are referenced to the deuterated solvent peaks. Coupling values J are given in Hz. Attached proton test (APT) NMR studies were used for the assignment of the 13C peaks as CH3, CH2, CH and Cq (quaternary). The MALDI-TOF mass spectrum (+ve mode) was recorded on a Bruker Autoflex III Smartbeam instrument (Bruker). Cyclic voltammetry (CV) measurements were performed on a Princeton Applied Research 263A potentiostat/galvanostat apparatus (Princeton Applied Research, Oak Ridge, TN, USA). The elemental analysis was run by the London Metropolitan University Elemental Analysis Service on a Perkin Elmer 2400 Elemental analyzer (Perkin Elmer, Waltham, MA, USA). 5,5′-Dibromo-4,4′-diphenyl-2,2′-bithiazole (7) [11] and 9-(2-ethylhexyl)-3-(tributylstannyl)-9H-carbazole (8) [12] were prepared according to the literature procedures.

5,5′-Bis [9-(2-ethylhexyl)-9H-carbazol-3-yl]-4,4′-diphenyl-2,2′-bithiazole (6)

To a stirred mixture of 5,5′-dibromo-4,4′-diphenyl-2,2′-bithiazole (7) (15.0 mg, 0.031 mmol) in anhyd. toluene (1 mL) at, ca., 20 °C, 9-(2-ethylhexyl)-3-(tributylstannyl)-9H-carbazole (8) (52.9 mg, 0.093 mmol) and Pd(Ph3P)2Cl2 (1.1 mg, 0.0016 mmol) were added. The solution was then deaerated by bubbling Ar gas into the reaction mixture for 10 min and then the mixture was heated at reflux under Ar, until no starting material remained (TLC, 2 h). On cooling to, ca., 20 °C, t-BuOMe (10 mL) was added and the mixture was washed with saturated KF (aq) to remove organotin residues, dried (Na2SO4), adsorbed onto silica and chromatographed (n-hexane/CH2Cl2, 60:40 v/v) to give the title compound 6 (23 mg, 85%) as orange needles, mp 75–77 °C (from MeCN); Rf 0.40 (n-hexane/CH2Cl2, 60:40 v/v); (found: C, 79.42; H, 6.55; N, 6.50. C58H58N4S2 requires C, 79.59; H, 6.68; N, 6.40%); λmax (CH2Cl2)/nm 241 (log ε 3.78), 265 inf (3.54), 298 inf (3.43), 363 inf (3.15), 383 inf (3.25), 405 (3.30); νmax/cm−1 2955w, 2926m and 2855w (C-H), 1734m, 1684m, 1653m, 1647w, 1624w, 1599m, 1558m, 1506m, 1491m, 1462s, 1443m, 1414w, 1379w, 1348m, 1331m, 1319w, 1275m, 1256w, 1219m, 1204m, 1153m, 1125w, 936m, 914w, 887w, 851w, 802s, 768s, 746s, 729s; δH (500 MHz; CDCl3) 8.20 (2H, d, 4JH-H 1.4, Ar CH), 8.02 (2H, d, 3JH-H 7.7, Ar CH), 7.69–7.67 (4H, m, Ar CH), 7.50–7.47 (4H, m, Ar CH), 7.42 (2H, d, 3JH-H 8.1, Ar CH), 7.35 (2H, d, 3JH-H 8.6, Ar CH), 7.32–7.29 (6H, m, Ar CH), 7.24 (2H, dd, 3JH-H 7.2, 7.2, Ar CH), 4.19–4.17 (4H, m, CH2), 2.12–2.04 (2H, m, CH), 1.46–1.24 (16H, m, CH2), 0.95 (6H, t, 3JH-H 7.4, CH3), 0.88 (6H, t, 3JH-H 7.2, CH3); δC (125 MHz; CDCl3) 158.5 (Cq), 150.1 (Cq), 141.3 (Cq), 140.8 (Cq), 136.6 (Cq), 134.9 (Cq), 129.1 (CH), 127.8 (CH), 127.3 (CH), 126.1 (CH), 123.1 (Cq), 122.5 (Cq), 121.5 (Cq), 120.4 (CH), 119.2 (CH), 109.3 (CH), 109.2 (CH), 47.6 (CH2), 39.4 (CH), 31.0 (CH2), 28.8 (CH2), 24.4 (CH2), 23.0 (CH2), 14.0 (CH3), 10.9 (CH3); m/z (MALDI-TOF) 875 (MH+, 21%), 776 (MH+-C7H15, 100).

Supplementary Materials

The following supporting information can be downloaded online: molfile, Figure S1: Cyclic voltammogram of bithiazole 6; Figure S2: UV-vis absorption spectrum of bithiazole 6, 1H, 13C NMR and mass spectra.

Author Contributions

A.S.K. designed and performed the experiments, analyzed the data and wrote the paper; P.A.K. conceived the experiments. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the University of Cyprus [Internal Grant “Thiadiazine-Based Organic Photovoltaics”] and the Cyprus Research Promotion Foundation [Grants: ΣTPATHII/0308/06, NEKYP/0308/02 ΥΓEIA/0506/19 and ENIΣX/0308/83].

Acknowledgments

The authors thank Felix Hermerschmidt and Sachetan Tuladhar for initial OPV device studies using the title molecule in combination with P3HT in BHJ solar cells. P.A.K. and A.S.K. thank the following organizations and companies in Cyprus for generous donations of chemicals and glassware: the State General Laboratory, the Agricultural Research Institute, the Ministry of Agriculture, MedoChemie Ltd., Medisell Ltd. and Biotronics Ltd. Furthermore, we thank the A.G. Leventis Foundation for helping to establish the NMR facility at the University of Cyprus.

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Chotera-Ouda, A.; Wróblewska, A.; Tokarz, P.; Stevens, C.V. Thiazoles. In Comprehensive Heterocyclic Chemistry IV; Koutentis, P.A., StC Black, D., Cossy, J., Stevens, C.V., Eds.; Elsevier: Oxford, UK, 2022; Volume 4, Chapter 4.06; pp. 530–623. [Google Scholar] [CrossRef]
  2. Chen, B.; Heal, W. Thiazoles. In Comprehensive Heterocyclic Chemistry III; Zhdankin, V.V., Katritzky, A.R., Ramsden, C.A., Scriven, E.F.V., Taylor, R.J.K., Eds.; Elsevier: Oxford, UK, 2008; Volume 4, Chapter 4.06; pp. 635–754. [Google Scholar] [CrossRef]
  3. Koutentis, P.A.; Ioannidou, H.A. Thiazoles. In Science of Synthesis Knowledge Updates 2010/1; Schaumann, E., Ed.; Thieme Chemistry: Stuttgart, Germany, 2010; Volume 11, Product Class 17; pp. 267–391. [Google Scholar]
  4. Fattal-Valevski, A. Thiamine (Vitamin B1). J. Evid. Based Complement. Altern. Med. 2011, 16, 12–20. [Google Scholar] [CrossRef]
  5. Lea, A.P.; Faulds, D. Ritonavir. Drugs 1996, 52, 541–546. [Google Scholar] [CrossRef] [PubMed]
  6. Takagi, T.; Takeda, M.; Fujihara, A.; Yashima, Y. General pharmacological properties of a new potent H2-blocker, famotidine (YM-11170). Pharmacometrics 1983, 26, 599–611. [Google Scholar]
  7. Umezawa, H.; Maeda, K.; Takeuchi, T.; Okami, Y. New antibiotics, bleomycin A and B. J. Antibiot. 1966, 19, 200–209. [Google Scholar]
  8. Ando, S.; Murakami, R.; Nishida, J.; Tada, H.; Inoue, Y.; Tokito, S.; Yamashita, Y. n-Type organic field-effect transistors with very high electron mobility based on thiazole oligomers with trifluoromethylphenyl Groups. J. Am. Chem. Soc. 2005, 127, 14996–14997. [Google Scholar] [CrossRef] [PubMed]
  9. Chen, L.; Huang, L.; Yang, D.; Ma, S.; Zhou, X.; Zhang, J.; Tu, G.; Li, C. A non-fullerene acceptor with all “A” units realizing high open-circuit voltage solution-processed organic photovoltaics. J. Mater. Chem. A 2014, 2, 2657–2662. [Google Scholar] [CrossRef]
  10. Kalogirou, A.S.; Michaelidou, S.S.; White, A.J.P.; Koutentis, P.A. Transformation of 2-(4-chloro-5H-1,2,3-dithiazol-5-ylideneamino)-6-ethoxy-4-phenylpyridine-3,5-dicarbonitrile into 4-aminopyrido[2,3-d]pyrimidines and 2-(pyrid-2-yl)guanidines. Tetrahedron 2015, 71, 1799–1807. [Google Scholar] [CrossRef]
  11. Koyioni, M.; Koutentis, P.A. Synthesis of 5,5′-Diarylimino Quinoidal 2,2′-Bithiazoles. Org. Lett. 2017, 19, 174–177. [Google Scholar] [CrossRef] [PubMed]
  12. Hermerschmidt, F.; Kalogirou, A.S.; Min, J.; Zissimou, G.A.; Tuladhar, S.M.; Ameri, T.; Faber, H.; Itskos, G.; Choulis, S.A.; Anthopoulos, T.D.; et al. 4H-1,2,6-Thiadiazin-4-one-containing small molecule donors and additive effects on their performance in solution-processed organic solar cells. J. Mater. Chem. C 2015, 3, 2358–2365. [Google Scholar] [CrossRef]
  13. Chochos, C.L.; Kalogirou, A.S.; Ye, T.; Tatsi, E.; Katsouras, A.; Zissimou, G.A.; Gregoriou, V.G.; Avgeropoulos, A.; Koutentis, P.A. 4H-1,2,6-Thiadiazine-containing donor–acceptor conjugated polymers: Synthesis, optoelectronic characterization and their use in organic solar cells. J. Mater. Chem. C 2018, 6, 3658–3667. [Google Scholar] [CrossRef]
  14. Inoue, M.; Hayashi, K. Material for Photoelectric Conversion Element for Imaging, and Photoelectric Conversion Element. WO2023/140173, 27 July 2023. [Google Scholar]
  15. Chang, G.-P.; Chuang, C.-N.; Lee, J.-Y.; Chang, Y.-S.; Leung, M.-K.; Hsieh, K.-H. Synthesis and characterization of graft polystyrenes with para-substituted π-conjugated oligo(carbazole) and oligo(carbazole-thiophene) moieties for organic field-effect transistors. Polymer 2013, 54, 3548–3555. [Google Scholar] [CrossRef]
  16. Chen, S.; Ma, T.; Du, X.; Mo, M.; Wang, Z.; Cheng, X. D-A-D hexacatenar LCs containing bulky N-trialkoxylbenzyl carbazole caps with RGB emissions for full color palette and white LED applications. J. Mol. Liq. 2023, 373, 121239. [Google Scholar] [CrossRef]
  17. Aksoy, B.T.; Senocak, A.; Erol, I.; Saglam, M.F.; Kandemir, H.; Sengul, I.F.; Çoşut, B. Meso carbazole linked Bis-BODIPYs: Design, synthesis, structures and properties. Tetrahedron 2023, 147, 133666. [Google Scholar] [CrossRef]
  18. Findlater, M.; Swisher, N.S.; White, P.S. Synthesis and Structure of Boron–Bithiazole Complexes. Eur. J. Org. Chem. 2010, 2010, 5379–5382. [Google Scholar] [CrossRef]
  19. Sharma, G.D.; Shanap, T.S.; Patel, K.R.; El-Mansy, M.K. Photovoltaic properties of bulk heterojunction devices based on CuI-PVA as electron donor and PCBM and modified PCBM as electron acceptor. Mater. Sci.-Pol. 2012, 30, 10–16. [Google Scholar] [CrossRef]
Figure 1. Thiamine, famotidine and the parent structures of 2,2′- and 2,4′-bithiazoles.
Figure 1. Thiamine, famotidine and the parent structures of 2,2′- and 2,4′-bithiazoles.
Molbank 2024 m1761 g001
Figure 2. Structures of quinoidal (2E,5Z,5′Z)-2,2′-bithiazoles 1 and 2.
Figure 2. Structures of quinoidal (2E,5Z,5′Z)-2,2′-bithiazoles 1 and 2.
Molbank 2024 m1761 g002
Figure 3. General structures of carbazole-bound 2,2′-bithienyls 3 and PubChem-reported carbazole-bound 2,2′-bithiazoles 4 and 5.
Figure 3. General structures of carbazole-bound 2,2′-bithienyls 3 and PubChem-reported carbazole-bound 2,2′-bithiazoles 4 and 5.
Molbank 2024 m1761 g003
Scheme 1. Synthesis of (l,u)-5,5′-bis[9-(2-ethylhexyl)-9H-carbazol-3-yl]-4,4′-diphenyl-2,2′-bithiazole, (l,u)-6.
Scheme 1. Synthesis of (l,u)-5,5′-bis[9-(2-ethylhexyl)-9H-carbazol-3-yl]-4,4′-diphenyl-2,2′-bithiazole, (l,u)-6.
Molbank 2024 m1761 sch001
Table 1. UV-vis and CV of 5,5′-bis[9-(2-ethylhexyl)-9H-carbazol-3-yl]-4,4′-diphenyl-2,2′-bithiazole (6). All the values correspond to peak onsets.
Table 1. UV-vis and CV of 5,5′-bis[9-(2-ethylhexyl)-9H-carbazol-3-yl]-4,4′-diphenyl-2,2′-bithiazole (6). All the values correspond to peak onsets.
Eox
(V)
λmax
(nm)
Egopt
(eV)
EHOMO
(eV)
Ered
(V)
ELUMO
(eV)
Egechem
(eV)
0.744722.63−5.84−1.42−3.682.16
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MDPI and ACS Style

Kalogirou, A.S.; Koutentis, P.A. 5,5′-Bis[9-(2-ethylhexyl)-9H-carbazol-3-yl]-4,4′-diphenyl-2,2′-bithiazole. Molbank 2024, 2024, M1761. https://doi.org/10.3390/M1761

AMA Style

Kalogirou AS, Koutentis PA. 5,5′-Bis[9-(2-ethylhexyl)-9H-carbazol-3-yl]-4,4′-diphenyl-2,2′-bithiazole. Molbank. 2024; 2024(1):M1761. https://doi.org/10.3390/M1761

Chicago/Turabian Style

Kalogirou, Andreas S., and Panayiotis A. Koutentis. 2024. "5,5′-Bis[9-(2-ethylhexyl)-9H-carbazol-3-yl]-4,4′-diphenyl-2,2′-bithiazole" Molbank 2024, no. 1: M1761. https://doi.org/10.3390/M1761

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