Synthesis and optical properties of fluorene-azulene π-conjugated polymers
Abstract
The non-alternant aromatic hydrocarbon azulene as a potential building block for the creation of new polymer conjugated materials is attracting more and more attention due to its unique chemical structure, optical and physico-chemical properties. The azulene conjugated polymers were synthesized by the interaction of 1,3-dibromoazulene or 2,7-bis(3-bromoazulene1-yl)-9,9-dihexyl-9H-fluorene with 2,2’-(9,9-dihexylfluorene-2,7-diyl)bis(1,3,2-dioxaborolan) under the conditions of the Suzuki cross-coupling reaction: poly[2,7-(9,9-dihexylfluorenyl)- alt-(1ꞌ,3ꞌ-azulenyl)] 3 and poly[1,3-bis(9ꞌ,9ꞌ-dihexylfluorene-2ꞌ-yl)azulenyl]-alt-[1ꞌꞌ,3ꞌꞌ-azulenyl] 5. The photophysical and thermal properties of the obtained fluorene-azulene polymers were characterized by UF-Vis and fluorescence spectroscopy, as well as methods of thermogravimetric analysis and differential scanning calorimetry. It was found that polymers 3 and 5 do not emit in a neutral state in various organic solvents. However, they become fluorescent on treatment with trifluoroacetic acid in tetrahydrofuran. The “activation” of fluorescence in protonated azulene copolymers 3-H+ and 5-H+ occurs due to the formation of the 6π-electron aromatic azulene cation, which changes the overall electronic character, in particular, the levels of the frontal molecular orbitals of the HOMO and LUMO, and then the band gap. The obtained results demonstrate that the inclusion of azulene structural units in the conjugated polymer strucrure has great potential for the development of new protonic organic functional materials.
References
2 Lash TD, Colby DA, Graham SR, Chaney ST (2004) J Org Chem 69:8851-8864. Crossref
3 Wakabayashi S, Kato Y, Mochizuki K, Suzuki R, Matsumoto M, et al. (2007) J Org Chem 72:744-749. http://doi.org/10.1021/jo061684h
4 Amatatsu Y (2007) J Phys Chem A 111:5327-5332. Crossref
5 Möllerstedt H, Piqueras MC, Crespo R, Ottosson H (2004) J Am Chem Soc 126:13938-13939. Crossref
6 Peart PA, Repka LM, Tovar JD (2008) European J Org Chem 2008:219-2206. Crossref
7 Shoji T, Ito S, Toyota K, Yasunami M, Morita N (2008) Chemistry – A European Journal 14:8398-8408. Crossref
8 Ito S, Kubo T, Morita N, Ikoma T, Tero-Kubota S, et al. (2005) J Org Chem 70:2285-2293. Crossref
9 Ito S, Kubo T, Morita N, Ikoma T, Tero-Kubota S, et al. (2003) J Org Chem 68:9753-9762. Crossref
10 Colby DA, Ferrence GM, Lash TD (2004) Angewandte Chemie International Edition 43:1346-1349. Crossref
11 López-Alled CM, Park SJ, Lee DJ, Murfin LC, Kociok-Köhn G et al. (2021) Chemical Communications 57:10608-10611. Crossref
12 Xin H, Hou B, Gao X (2021) Acc Chem Res 54:1737-1753. Crossref
13 Anderson AG, Steckler BM (1959) J Am Chem Soc 81:4941-4946. Crossref
14 Xin H, Gao X (2017) Chempluschem 82:945-956. Crossref
15 Tomin VI, Włodarkiewicz A (2018) J Lumin 198:220-225. Crossref
16 Yushchenko O, Licari G, Mosquera-Vazquez S, Sakai N, Matile S et al. (2015) J Phys Chem Lett 6:2096-2100. Crossref
17 Nenov A, Borrego-Varillas R, Oriana A, Ganzer L, Segatta F et al. (2018) J Phys Chem Lett 9:1534-1541. Crossref
18 Demchenko AP, Tomin VI, Chou P-T (2017) Chem Rev 117:13353-13381. Crossref
19 del Valle JC, Catalán J (2019) Physical Chemistry Chemical Physics 21:10061-10069. Crossref
20 Behera SK, Park SY, Gierschner J (2021) Angewandte Chemie International Edition 60:22624-22638. Crossref
21 Dunlop D, Ludvíková L, Banerjee A, Ottosson H, Slanina T (2023) J Am Chem Soc 145:21569-21575. Crossref
22 Wang F, Lai Y-H (2003) Macromolecules 36:536-538. Crossref
23 Wang F, Lai Y-H, Han M-Y (2004) Macromolecules 37:3222-3230. Crossref
24 Mrozek T, Görner H, Daub J (2001) Chemistry (Easton) 7:1028-1040. Crossref
25 Dong J-X, Zhang H-L (2016) Chinese Chemical Letters 27:1097-1104. Crossref
26 Ou L, Zhou Y, Wu B, Zhu L (2019) Chinese Chemical Letters 30:1903-1907. Crossref
27 Kurotobi K, Kim KS, Noh SB, Kim D, Osuka A (2006) Angewandte Chemie International Edition 45:3944-3947. Crossref
28 Cristian L, Sasaki I, Lacroix PG, Donnadieu B, Asselberghs I, et al. (2004) Chemistry of Materials 16:3543-3551. Crossref
29 Ito S, Inabe H, Morita N, Ohta K, Kitamura T, Imafuku K (2003) J Am Chem Soc 125:1669-1680. Crossref
30 Yamaguchi Y, Takubo M, Ogawa K, Nakayama K, Koganezawa T et al. (2016) J Am Chem Soc 138:11335-11343. Crossref
31 Nishimura H, Ishida N, Shimazaki A, Wakamiya A, Saeki A et al. (2015) J Am Chem Soc 137:15656-15659. Crossref
32 Zhou Y, Zou Q, Qiu J, Wang L, Zhu L (2018) J Phys Chem Lett 9:550-556. Crossref
33 Zhou Y, Zhu L (2018) Chemistry – A European Journal 24:10306-10309. Crossref
34 Kihara N, Nakayama H, Fukutomi T (1997) Macromolecules 30:6385-6387. Crossref
35 Wang F, Lai Y-H, Kocherginsky NM, Kosteski YuYu (2003) Org Lett 5:995-998. Crossref
36 Wang F, Lai Y-H (2003) Macromolecules 36:536-538. Crossref
37 Wang F, Lai Y-H, Han MY (2003) Org Lett 5:4791-4794. Crossref
38 Rentzepis PM (1969) Chem Phys Lett 3:717-720. Crossref
39 Bearpark MJ, Bernardi F, Clifford S, Olivucci M, Robb MA, et al. (1996) J Am Chem Soc 118:169-175. Crossref
40 Sprutta N, Siczek M, Latos-Grażyński L, Pawlicki M, Szterenberg L, Lis T (2007) J Org Chem 72:9501-9509. Crossref
41 Ito S, Ando M, Nomura A, Morita N, Kabuto C et al. (2005) J Org Chem 70:3939-3949. Crossref
42 Ito S, Nomura A, Morita N, Kabuto C, Kobayashi H et al. (2002) J Org Chem 67:7295-7302. Crossref
43 Ito S, Kikuchi S, Okujima T, Morita N, Asao T (2001) J Org Chem 66:2470-2479. Crossref
44 Jönsson L, Fex T, Svensson C (1981) Acta Chem Scand 35b:683-689. Crossref
45 Waltman RJ, Bargon J (1986) Can J Chem 64:76-95. Crossref
46 Merkhatuly N, Iskanderov AN, Zhokizhanova SK, Kokibasova GT (2023) Rus J Org Chem 59:782-786. Crossref
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