Synthesis and Characterization of Phenothiazine-based Schiff Bases as Visible Light Photoinitiators

doi:10.7503/cjcu20210857

Abstract

Abstract:

In order to construct photoinitiators with strong molar extinction coefficient in the visible light region， four novel D-π-A type phenothiazine-based derivatives have been designed and synthesized. The structures were cha-racterized by nuclear magnetic resonance and high-resolution mass spectrum. These phenothiazine derivatives， as a strong electron-donating group， can easily undergo photo-induced electron transfer with iodonium salt（Iod）， thereby initiating the radical and cationic photopolymerization. Interestingly， the prepared photoinitiators exhibit the characteristics of charge transfer in the ground and excited states and have the strong molar extinction coefficient of 10⁴ L·mol^-1·cm^-1 in the spectral range of 350—450 nm， and have the red shifts about 50 nm compared with the commercial photoinitiator 2-isopropylthioxanthone（ITX）， well matching the emitting spectra of the popularly used 405 nm LED light source. Theoretical calculations of molecular orbitals also explain the excellent optical properties of photoinitiators. The two-component initiating system has faster initiation efficiency and higher conversion rate than that of commercial photoinitiator ITX/Iod for free radical as well as cation photopolymerizations by changing different conditions of the formulas. The formula with PI（0.2%， molar fraction） and Iod（2%， molar fraction） exhibit the best curing effect. An photoinduced electron transfer（PET） mechanism was established based on steady-state photolysis experiments， and electron spin resonance spectroscopy experiment which captured the benzene radicals. The free energy changes（ΔG_et） were measured by cyclic voltammetry（CV） experiments which proved the possibility of PET mechanism thermodynamically. Under irradiation， APN/Iod undergo the electronic transfer and the formed benzene radicals initiate polymerization of acrylates， and the active species is produced to initiate cationic polymerization of epoxy at the same time. In addition， the printing of fluorescent light-emitting devices was successfully carried out through the technology of Digital Light Processing（DLP） 3D printing.

Key words: Phenothiazine, Schiff base, Photoinitiator, Electron transfer

CLC Number:

O631

TrendMD:

XU Dandan, ZOU Xiucheng, LUO Jing, LIU Ren. Synthesis and Characterization of Phenothiazine-based Schiff Bases as Visible Light Photoinitiators[J]. Chem. J. Chinese Universities, 2022, 43(4): 20210857.

Figures/Tables 10

References 27

1	Mironi⁃Harpaz I.， Wang D. Y.， Venkatraman S.， Seliktar D.， Acta Biomater.， 2012， 8（5）， 1838—1848
2	Fisher J. P.， Dean D.， Engel P. S.， Mikos A. G.， Annu. Rev.， Mater. Res.， 2001， 31（1）， 171—181
3	Zhu P.， Lin Z.， Goddard J. M.， Food Chem.， 2019， 286， 154—159
4	Li J.， Li H.， Fok A. S. L.， Watts D. C.， Dent. Mater. 2009， 25（7）， 829—836
5	Erdur S.， Yilmaz G.， Goen Colak D.， Cianga I.， Yagci Y.， Macromolecules， 2014 ， 47（21）， 7296—7302
6	Huang X.， Zhang Y.， Shi M.， Zhang Y.， Zhao Y.， Polym. Chem.， 2019， 10（18）， 2273—2281
7	Li Z.， Zou X.， Zhu G.， Liu X.， Liu R.， ACS Appl. Mater. Interfaces， 2018， 10（18）， 16113—16123
8	Tadashi Gomi M. T.， Chem. Pharm. Bull.， 2002， 43， 2091
9	Abdallah M.， Dumur F.， Hijazi A.， Rodeghiero G.， Gualandi A.， Cozzi P. G.， Lalevée J.， J. Polym. Sci.， 2020， 58（8）， 1115—1129
10	Xie C.， Wang Z.， Liu Y.， Song L.， Liu L.， Wang Z.， Yu Q.， Prog. Org. Coatings， 2019， 135（5）， 34—40
11	Abdallah M.， Hijazi A.， Lin J. T.， Graff B.， Dumur F.， Lalevée J.， ACS Appl. Polym. Mater.， 2020， 2（7）， 2769—2780
12	Pigot C.， Noirbent G.， Brunel D.， Dumur F.， Eur. Polym. J.， 2020， 133（4）， 109797
13	Tehfe M. A.， Dumur F.， Graff B.， Gigmes D.， Fouassier J. P.， Lalevée J.， Macromolecules， 2013， 46（9）， 3332—3341
14	Zhang Y.， Yan Y.， Xia S.， Wan S.， Steenwinkel T. E.， Medford J.， Durocher E.， Luck R. L.， Werner T.， Liu H.， ACS Appl. Mater. Interfaces， 2020， 12（18）， 20172—20179
15	Qiu W.， Hu P.， Zhu J.， Liu R.， Li Z.， Hu Z.， Chen Q.， Dietliker K.， Liska R.， ChemPhotoChem.， 2019， 3（11）， 1090—1094
16	Li Z.， Zou X.， Shi F.， Liu R.， Yagci Y.， Nat. Commun.， 2019， 10（1）， 3560
17	Tehfe M. A.， Dumur F.， Graff B.， Gigmes D.， Fouassier J. P.， Lalevée J.， Macromolecules.， 2013， 46（9）， 3332—3341
18	Podlesný J.， Pytela O.， Klikar M.， Jelínková V.， Kityk I. V.， Ozga K.， Jedryka J.， Rudysh M.， Bureš F.， Org. Biomol. Chem.， 2019， 17（14）， 3623—3634
19	Bureš F.， RSC Adv.， 2014， 4（102）， 58826—58851
20	Pascal S.， Getmanenko Y. A.， Zhang Y.， Davydenko I.， Ngo M. H.， Pilet G.， Redon S.， Bretonnière Y.， Maury O.， Ledoux⁃Rak I.， Barlow S.， Marder S. R.， Andraud C.， Chem. Mater.， 2018， 30（10）， 3410—3418
21	Revoju S.， Matuhina A.， Canil L.， Salonen H.， Hiltunen A.， Abate A.， Vivo P.， J. Mater. Chem. C， 2020， 8（44）， 15486—15506
22	Mayer M.， J. Am. Chem. Soc.， 2004， 126（13）， 4453—4460
23	Zhou T. F.， Ma X. Y.， Han W. X.， Guo X. P.， Gu R. Q.， Yu L. J.， Li J.， Zhao Y. M.， Wang T.， Polym. Chem.， 2016， 7（31）， 5039—5049
24	Gomurashvili Z.， Crivello J. V.， Macromolecules， 2002， 35（8）， 2962—2969
25	Kasapoglu F.， Yagci Y.， Rapid Commun.， 2002， 23（9）， 567
26	Antonov L.， Kamada K.， Ohta K.， Kamounah F. S.， Phys. Chem. Chem. Phys.， 2003， 5（6）， 1193—1197
27	Trucks G. W.， Frisch M. J.， Schlegel H. B.， Scuseria G. E.， Robb M. A.， Cheeseman J. R.， Scalmani G.， Barone V.， Mennucci B.， Petersson G. A.， Nakatsuji H.， Caricato M.， Li X.， Hratchian H. P.， Izmaylov A. F.， Bloino J.， Zheng G.， Sonnenberg J. L.， Hada M.， Ehara M.， Toyota K.， Fukuda R.， Hasegawa J.， Ishida M.， NakajimaT.， Honda Y.， Kitao O.， Nakai H.， Vreven T.， Montgomery J. A.， Jr. Peralta， J. E. Ogliaro， F. Bearpark， M. Heyd， J. J. Brothers， E. Kudin， K. N. Staroverov V. N.， Keith T.， Kobayashi R.， Normand J.， Raghavachari K.， Rendell A.， Burant J. C.， Iyengar S. S.， Tomasi J.， Cossi M.， Rega N.， Millam J. M.， Klene M.， Knox J. E.， Cross J. B.， Bakken V.， Adamo C.， Jaramillo J.， Gomperts R.， Stratmann R. E.， Yazyev O.， Austin A. J.， Cammi R.， Pomelli C.， Ochterski J. W.， Martin R. L.， Morokuma K.， Zakrzewski V. G.， Voth G. A.， Salvador P.， Dannenberg J. J.， Dapprich S.， Daniels A. D.， Farkas O.， Foresman J. B.， Ortiz J. V.， Cioslowski J.， Fox D. J.， Gaussian 09， Revision B.01， Gaussian， Inc.， Wallingford， CT， 2010

Photoinitiator	λ_max/nm	10⁴ε₄₀₅/（L·mol^-1·cm^-1）	10⁴ε_max/（L·mol^-1·cm^-1）	λ_ex/nm	λ_{em max}/nm
APH	384	0.81	1.01	384	545
APC	399	0.97	0.98	399	585
APF	393	0.96	1.02	393	572
APN	403	1.05	1.06	403	603

Photoinitiator	λ_max/nm	10⁴ε₄₀₅/（L·mol^-1·cm^-1）	10⁴ε_max/（L·mol^-1·cm^-1）	λ_ex/nm	λ_{em max}/nm
APH	384	0.81	1.01	384	545
APC	399	0.97	0.98	399	585
APF	393	0.96	1.02	393	572
APN	403	1.05	1.06	403	603

Photoinitiator	E_ox/V	E₀₀/eV	λ/nm	ΔG_et/eV
APH	1.70	2.79	443	-0.21
APC	1.35	2.71	458	-0.48
APF	1.41	2.73	455	-0.42
APN	1.51	2.66	466	-0.27

Photoinitiator	E_ox/V	E₀₀/eV	λ/nm	ΔG_et/eV
APH	1.70	2.79	443	-0.21
APC	1.35	2.71	458	-0.48
APF	1.41	2.73	455	-0.42
APN	1.51	2.66	466	-0.27

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