Dithienothiazine Copolymers – Synthesis and Electronic Properties of Novel Redox-Active Fluorescent Polymers

Abstract

Dithienothiazine copolymers are efficiently obtained by Suzuki polymerization or in situ lithiation–Negishi polymerization in good to excellent yields. Gel permeation chromatography was applied to characterize the dispersities and degrees of polymerization of these novel materials. Thermogravimetric analysis shows that the copolymers are stable towards side-chain cleavage up to 200 °C. The materials are deep red to black amorphous solids or resins and their absorption and emission spectra in solution reveal broad absorption bands in the visible and orange to deep red luminescence upon UV excitation. According to the optical band gaps these novel copolymers qualify as a new class of low band gap organic semiconductors.

Key words

fluorescence - heterocycles - low band gap polymers - Negishi coupling - polymerization - Suzuki coupling

• References

• 1a MacDiarmid AG. Angew. Chem. Int. Ed. 2001; 40: 2581
• 1b Kiess HG. Conjugated conducting polymers. Vol. 102. Springer; Heidelberg: 1992
• 2 Rasmussen SC. ChemPlusChem 2020; 85: 1412
• 3a Fratini S, Nikolka M, Salleo A, Schweicher G, Sirringhaus H. Nat. Mater. 2020; 19: 491
• 3b Wang C, Zhang X, Hu W. Chem. Soc. Rev. 2020; 49: 653
• 3c Bronstein H, Nielsen CB, Schroeder BC, McCulloch I. Nat. Rev. Chem. 2020; 4: 66
• 3d Bhosale ME, Chae S, Kim JM, Choi J.-Y. J. Mater. Chem. A 2018; 6: 19885
• 3e Bujak P, Kulszewicz-Bajer I, Zagorska M, Maurel V, Wielgus I, Pron A. Chem. Soc. Rev. 2013; 42: 8895
• 3f Dong H, Zhu H, Meng Q, Gong X, Hu W. Chem. Soc. Rev. 2012; 41: 1754
• 4a Jayakumar J, Chou H.-H. ChemCatChem 2020; 12: 689
• 4b Dai C, Liu B. Energy Environ. Sci. 2020; 13: 24
• 5a Li J, Pu K. Chem. Soc. Rev. 2019; 48: 38
• 5b Nezakati T, Seifalian A, Tan A, Seifalian AM. Chem. Rev. 2018; 118: 6766
• 6a Mazzio KA, Luscombe CK. Chem. Soc. Rev. 2015; 44: 78
• 6b Facchetti A. Chem. Mater. 2011; 23: 733
• 6c Cheng Y.-J, Yang S.-H, Hsu C.-S. Chem. Rev. 2009; 109: 5868
• 7 Ying L, Huang F, Bazan GC. Nat. Commun. 2017; 8: 14047
• 8 Wang J, Liu K, Ma L, Zhan X. Chem. Rev. 2016; 116: 14675
• 9 Cinar ME, Ozturk T. Chem. Rev. 2015; 115: 3036
• 10 Aitken RA, Aitken KM. 1,4-Thiazines and their Benzo Derivatives. In: Comprehensive Heterocyclic Chemistry III. Katritzky AR, Ramsden AC, Scriven EF. .. V, Taylor RJ. .. K. Elsevier; Amsterdam: 2008: 607
• 11 Pereţeanu IS, Müller TJ. J. Org. Biomol. Chem. 2013; 11: 5127
• 12a Park Y, Kim B, Lee C, Hyun A, Jang S, Lee J.-H, Gal Y.-S, Kim TH, Kim K.-S, Park J. J. Phys. Chem. C 2011; 115: 4843
• 12b Salunke JK, Wong FL, Feron K, Manzhos S, Lo MF, Shinde D, Patil A, Lee CS, Roy VA. L, Sonar P, Wadgaonkar PP. J. Mater. Chem. C 2016; 4: 1009
• 12c Qu B, Chen Z, Liu Y, Cao H, Xu S, Cao S, Lan Z, Wang Z, Gong Q. J. Phys. D: Appl. Phys. 2006; 39: 2680
• 12d Zhu Y, Champion RD, Jenekhe SA. Macromolecules 2006; 39: 8712
• 13a Urselmann D, Deilhof K, Mayer B, Müller TJ. J. Beilstein J. Org. Chem. 2016; 12: 2055
• 13b Müller TJ. J, Franz AW, ,Barkschat (née Krämer) C. S. Sailer M, Meerholz K, Müller D, Colsmann A, Lemmer U. Macromol. Symp. 2010; 287: 1
• 13c Sailer M, Franz AW, Müller TJ. J. Chem. Eur J. 2008; 14: 2602
• 14 May L, Müller TJ. J. Chem. Eur J. 2020; 26: 12111
• 15 May L, Müller TJ. J. Molecules 2020; 25: 2180
• 16a Dostert C, Müller TJ. J. Org. Chem. Front. 2015; 2: 481
• 16b Dostert C, Czajkowski D, Müller TJ. J. Synlett 2014; 25: 371
• 17 Nau J, Schneeweis AP. W, Müller TJ. J. Mater. Chem. Front. 2020; 4: 621
• 18 Mori S, Barth HG. Size Exclusion Chromatography. Springer Science & Business Media; Berlin: 2013
• 19 Netopilík M, Kratochvíl P. Polymer 2003; 44: 3431
• 20 Meyer T, Ogermann D, Pankrath A, Kleinermanns K, Müller TJ. J. J. Org. Chem. 2012; 77: 3704
• 21 Brutting W, Rieß W. Phys. J. 2008; 7: 33
• 22 Krämer CS, Zimmermann TJ, Sailer M, Müller TJ. J. Synthesis 2002; 1163
• 23 Heiskanen JP, Vivo P, Saari NM, Hukka TI, Kastinen T, Kaunisto K, Lemmetyinen HJ, Hormi OE. O. J. Org. Chem. 2016; 81: 1535
• 24 Han FS, Higuchi M, Kurth DG. Org. Lett. 2007; 9: 559
• 25 Zanello P. In Ferrocenes. A. Togni, A.; Hayashi, T. VCH; Weinheim: 1995: 317