Aggregation-induced emission and thermally activated delayed fluorescence of 2,6-diaminobenzophenones
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摘要
Exploration of novel organic luminophores that exhibit thermally activated delayed fluorescence(TADF) in the aggregated state is very crucial for advance of delayed luminescence-based applications such as time-gated bio-sensing and temperature sensing.We report herein that synthesis, photophysical properties, molecular and crystal structures, and theoretical calculations of 2,6-bis(diarylamino)benzophenones. Absorption spectra in solution and calculations using density functional theory(DFT) method revealed that the optical excitation took place through intramolecular charge-transfer from one diarylamino moiety to an aroyl group. While the benzophenones did not luminesce in solution, the solids of the benzophenones emitted green light with moderate-to-good quantum yields. Thus, the benzophenones exhibit aggregation-induced emission. Based on the lifetime measurement, the green emission of the solids was found to include TADF. The emergence of the TADF is supported by the small energy gap between the excited singlet and triplet states, which was estimated by time-dependent DFT calculations. Thin films of poly(methyl methacrylate) doped by the benzophenones also showed green prompt and delayed fluorescence whose lifetimes were in the order of microseconds. Linear correlation between logarithm value of TADF lifetime and temperature was observed with the benzophenone in powder, suggesting that the benzophenones can serve as molecular thermometers workable under aqueous conditions.
Exploration of novel organic luminophores that exhibit thermally activated delayed fluorescence(TADF) in the aggregated state is very crucial for advance of delayed luminescence-based applications such as time-gated bio-sensing and temperature sensing.We report herein that synthesis, photophysical properties, molecular and crystal structures, and theoretical calculations of 2,6-bis(diarylamino)benzophenones. Absorption spectra in solution and calculations using density functional theory(DFT) method revealed that the optical excitation took place through intramolecular charge-transfer from one diarylamino moiety to an aroyl group. While the benzophenones did not luminesce in solution, the solids of the benzophenones emitted green light with moderate-to-good quantum yields. Thus, the benzophenones exhibit aggregation-induced emission. Based on the lifetime measurement, the green emission of the solids was found to include TADF. The emergence of the TADF is supported by the small energy gap between the excited singlet and triplet states, which was estimated by time-dependent DFT calculations. Thin films of poly(methyl methacrylate) doped by the benzophenones also showed green prompt and delayed fluorescence whose lifetimes were in the order of microseconds. Linear correlation between logarithm value of TADF lifetime and temperature was observed with the benzophenone in powder, suggesting that the benzophenones can serve as molecular thermometers workable under aqueous conditions.
Exploration of novel organic luminophores that exhibit thermally activated delayed fluorescence(TADF) in the aggregated state is very crucial for advance of delayed luminescence-based applications such as time-gated bio-sensing and temperature sensing.We report herein that synthesis, photophysical properties, molecular and crystal structures, and theoretical calculations of 2,6-bis(diarylamino)benzophenones. Absorption spectra in solution and calculations using density functional theory(DFT) method revealed that the optical excitation took place through intramolecular charge-transfer from one diarylamino moiety to an aroyl group. While the benzophenones did not luminesce in solution, the solids of the benzophenones emitted green light with moderate-to-good quantum yields. Thus, the benzophenones exhibit aggregation-induced emission. Based on the lifetime measurement, the green emission of the solids was found to include TADF. The emergence of the TADF is supported by the small energy gap between the excited singlet and triplet states, which was estimated by time-dependent DFT calculations. Thin films of poly(methyl methacrylate) doped by the benzophenones also showed green prompt and delayed fluorescence whose lifetimes were in the order of microseconds. Linear correlation between logarithm value of TADF lifetime and temperature was observed with the benzophenone in powder, suggesting that the benzophenones can serve as molecular thermometers workable under aqueous conditions.
引文
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39 Schrum KF,Williams AM,Haerther SA,Ben-Amotz D.Anal Chem,1994,66:2788-2790
40 Fister JC,Rank D,Harris JM.Anal Chem,1995,67:4269-4275
41 Uchiyama S,Prasanna de Silva A,Iwai K.J Chem Educ,2006,83:720-727
42 Brites CDS,Lima PP,Silva NJO,Millán A,Amaral VS,Palacio F,Carlos LD.Nanoscale,2012,4:4799-4829
43 Mc Laurin EJ,Bradshaw LR,Gamelin DR.Chem Mater,2013,25:1283-1292
44 Bai T,Gu N.Small,2016,12:4590-4610
45 Uchiyama S,Gota C,Tsuji T,Inada N.Chem Commun,2017,53:10976-10992
2 Nakanotani H,Higuchi T,Furukawa T,Masui K,Morimoto K,Numata M,Tanaka H,Sagara Y,Yasuda T,Adachi C.Nat Commun,2014,5:4016
3 Zhang Q,Li B,Huang S,Nomura H,Tanaka H,Adachi C.Nat Photon,2014,8:326-332
4 Kaji H,Suzuki H,Fukushima T,Shizu K,Suzuki K,Kubo S,Komino T,Oiwa H,Suzuki F,Wakamiya A,Murata Y,Adachi C.Nat Commun,2015,6:8476
5 Marriott G,Clegg RM,Arndt-Jovin DJ,Jovin TM.Biophys J,1991,60:1374-1387
6 Carretero AS,Castillo AS,Gutiérrez AF.Crit Rev Anal Chem,2005,35:3-14
7 Suhling K,French PMW,Phillips D.Photochem Photobiol Sci,2005,4:13-22
8 Xiong X,Song F,Wang J,Zhang Y,Xue Y,Sun L,Jiang N,Gao P,Tian L,Peng X.J Am Chem Soc,2014,136:9590-9597
9 Shimizu M,Hiyama T.Chem Asian J,2010,5:1516-1531
10 Li Q,Li Z.Adv Sci,2017,4:1600484
11 Wong MY,Zysman-Colman E.Adv Mater,2017,29:1605444
12 Im Y,Kim M,Cho YJ,Seo JA,Yook KS,Lee JY.Chem Mater,2017,29:1946-1963
13 Yang Z,Mao Z,Xie Z,Zhang Y,Liu S,Zhao J,Xu J,Chi Z,Aldred MP.Chem Soc Rev,2017,46:915-1016
14 Tao Y,Yuan K,Chen T,Xu P,Li H,Chen R,Zheng C,Zhang L,Huang W.Adv Mater,2014,26:7931-7958
15 Chen B,Sun X,Evans RE,Zhou R,Demas JN,Trindle CO,Zhang G.J Phys Chem A,2015,119:8854-8859
16 Xu S,Liu T,Mu Y,Wang YF,Chi Z,Lo CC,Liu S,Zhang Y,Lien A,Xu J.Angew Chem Int Ed,2015,54:874-878
17 Xie Z,Chen C,Xu S,Li J,Zhang Y,Liu S,Xu J,Chi Z.Angew Chem Int Ed,2015,54:7181-7184
18 Gan S,Luo W,He B,Chen L,Nie H,Hu R,Qin A,Zhao Z,Tang BZ.J Mater Chem C,2016,4:3705-3708
19 Furue R,Nishimoto T,Park IS,Lee J,Yasuda T.Angew Chem Int Ed,2016,55:7171-7175
20 Tsujimoto H,Ha DG,Markopoulos G,Chae HS,Baldo MA,Swager TM.J Am Chem Soc,2017,139:4894-4900
21 Guo J,Li X-L,Nie H,Luo W,Gan S,Hu S,Hu R,Qin A,Zhao Z,Su S-J,Tang BZ.Adv Funct Mater,2017,1606458
22 Wang T,Wu Z,Sun W,Jin S,Zhang X,Zhou C,Jiang J,Luo Y,Zhang G.J Phys Chem A,2017,121:7183-7190
23 Guo J,Li XL,Nie H,Luo W,Hu R,Qin A,Zhao Z,Su SJ,Tang BZ.Chem Mater,2017,29:3623-3631
24 Shimizu M,Takeda Y,Higashi M,Hiyama T.Angew Chem Int Ed,2009,48:3653-3656
25 Shimizu M,Asai Y,Takeda Y,Yamatani A,Hiyama T.Tetrahedron Lett,2011,52:4084-4089
26 Shimizu M,Takeda Y,Higashi M,Hiyama T.Chem Asian J,2011,6:2536-2544
27 Shimizu M,Kaki R,Takeda Y,Hiyama T,Nagai N,Yamagishi H,Furutani H.Angew Chem Int Ed,2012,51:4095-4099
28 Shimizu M,Tamagawa T.Eur J Org Chem,2015,2015:291-295
29 Shimizu M,Fukui H,Natakani M,Sakaguchi H.Eur J Org Chem,2016,2016:5950-5956
30 Shimizu M,Fukui H,Shigitani R.Jnl Chin Chem Soc,2016,63:317-322
31 Shimizu M,Kimura A,Sakaguchi H.Eur J Org Chem,2016,2016:467-473
32 Shimizu M,Shigitani R,Nakatani M,Kuwabara K,Miyake Y,Tajima K,Sakai H,Hasobe T.J Phys Chem C,2016,120:11631-11639
33 Shimizu M,Kinoshita T,Shigitani R,Miyake Y,Tajima K.Mater Chem Front,2018,2:347-354
34 Shimizu M,Nakatani M.Eur J Org Chem,2017,2017:4695-4702
35 Mei J,Leung NLC,Kwok RTK,Lam JWY,Tang BZ.Chem Rev,2015,115:11718-11940
36 Mei J,Hong Y,Lam JWY,Qin A,Tang Y,Tang BZ.Adv Mater,2014,26:5429-5479
37 CCDC 1840378(for 1b)contains the supplementary crystallographic data for this paper.These data can be obtained free of charge from The Cambridge Crystallographic Data Centre
38 Frisch MJ,Trucks GW,Schlegel HB,Scuseria GE,Robb MA,Cheeseman JR,Scalmani G,Barone V,Mennucci B,Petersson GA,Nakatsuji H,Caricato M,Li X,Hratchian HP,Izmaylov AF,Bloino J,Zheng G,Sonnenberg JL,Hada M,Ehara M,Toyota K,Fukuda R,Hasegawa J,Ishida M,Nakajima T,Honda Y,Kitao O,Nakai H,Vreven T,Montgomery JA Jr,Peralta JE,Ogliaro F,Bearpark M,Heyd JJ,Brothers E,Kudin KN,Staroverov VN,Kobayashi R,Normand J,Raghavachari K,Rendell A,Burant JC,Iyengar SS,Tomasi J,Cossi M,Rega N,Millam JM,Klene M,Knox JE,Cross JB,Bakken V,Adamo C,Jaramillo J,Gomperts R,Stratmann RE,Yazyev O,Austin AJ,Cammi R,Pomelli C,Ochterski JW,Martin RL,Morokuma K,Zakrzewski VG,Voth GA,Salvador P,Dannenberg JJ,Dapprich S,Daniels AD,Farkas?,Foresman JB,Ortiz JV,Cioslowski J,Fox DJ.Gaussian 09,revision D.01.Wallingford:Gaussian,Inc.,2013
39 Schrum KF,Williams AM,Haerther SA,Ben-Amotz D.Anal Chem,1994,66:2788-2790
40 Fister JC,Rank D,Harris JM.Anal Chem,1995,67:4269-4275
41 Uchiyama S,Prasanna de Silva A,Iwai K.J Chem Educ,2006,83:720-727
42 Brites CDS,Lima PP,Silva NJO,Millán A,Amaral VS,Palacio F,Carlos LD.Nanoscale,2012,4:4799-4829
43 Mc Laurin EJ,Bradshaw LR,Gamelin DR.Chem Mater,2013,25:1283-1292
44 Bai T,Gu N.Small,2016,12:4590-4610
45 Uchiyama S,Gota C,Tsuji T,Inada N.Chem Commun,2017,53:10976-10992