Aqueous Photon Upconversion by Anionic Acceptors Self-Assembled on Cationic Bilayer Membranes with a Long Triplet Lifetime

Abstract

Anionic 9,10-diphenylanthracene chromophores electrostatically bound to cationic, chiral bilayer membranes show ordered self-assembly in water. The integrity of the chromophore-accumulated aqueous bilayer membranes is ensured by multiple hydrogen-bond networks introduced in the bilayer, which allowed adaptive accommodation of the guest chromophores at the inner surface of the bilayer while maintaining their cohesive interactions. The regular chromophore alignment in the aqueous assembly is confirmed by differential scanning calorimetry, circular dichroism, and circularly polarized luminescence spectra. Excitonic migration of triplet energy occurs among the chromophores densely organized at the inner surface of the bilayer, which lead to triplet–triplet annihilation-based photon upconversion (TTA-UC). This acceptor-bilayer self-assemblies show a notably long triplet lifetime of 8.0 ms, which allows TTA-UC at sufficiently low excitation light intensity. These results demonstrate the usefulness of the simple electrostatic accumulation approach for TTA-UC chromophores where the suitable molecular design of the TTA-UC chromophore-integrated bilayer membranes plays a key role.

Key words

self-assembly - photon upconversion - triplet - triplet–triplet annihilation - bilayer membranes - energy migration

• References and Notes

• 1 Rabinowitch E. , Govindjee. Photosynthesis. Wiley; New York: 1969
• 2 Blankenship RE. Molecular Mechanisms of Photosynthesis. Wiley-Blackwell; Hoboken, NJ: 2014
• 3 Kunitake T, Shimomura M, Hashiguchi Y, Kawanaka T. J. Chem. Soc. Chem. Commun. 1985; 833
• 4 Tamai N, Yamazaki T, Yamazaki I. Chem. Phys. Lett. 1988; 147: 25
• 5 Kimizuka N, Kunitake T. J. Am. Chem. Soc. 1989; 11: 3758
• 6 Morita T, Kimura S, Imanishi S. J. Am. Chem. Soc. 1999; 121: 581
• 7 Ajayaghosh A, George SJ, Praveen VK. Angew. Chem. Int. Ed. Engl. 2003; 42: 332
• 8 Kayser V, Turton DA, Aggeli A, Beevers A, Reid GD, Beddard GS. J. Am. Chem. Soc. 2004; 126: 336
• 9 Gao M, Paul S, Schwieters CD. , et al. J. Phys. Chem. C Nanomater. Interfaces 2015; 119: 13948
• 10 Sethy R, Kumar J, Métivier R. , et al. Angew. Chem. Int. Ed. Engl. 2017; 56: 15053
• 11 Nakashima T, Kimizuka N. Adv. Mater. 2002; 14: 1113
• 12 Baluschev S, Miteva T, Yakutkin V, Nelles G, Yasuda A, Wegner G. Phys. Rev. Lett. 2006; 97: 143903
• 13 Singh-Rachford TN, Castellano FN. Coord. Chem. Rev. 2010; 254: 2560
• 14 Zhao JZ, Ji SM, Guo HM. RSC Advances 2011; 1: 937
• 15 Monguzzi A, Tubino R, Hoseinkhani S, Campione M, Meinardi F. Phys. Chem. Chem. Phys. 2012; 14: 4322
• 16 Simon YC, Weder C. J. Mater. Chem. 2012; 22: 20817
• 17 Tayebjee MJY, McCamey DR, Schmidt TW. J. Phys. Chem. Lett. 2015; 6: 2367
• 18 Goldschmidt JC, Fischer S. Adv. Opt. Mater. 2015; 3: 510
• 19 Gray V, Moth-Poulsen K, Albinsson B, Abrahamsson M. Coord. Chem. Rev. 2018; 362: 54
• 20 Lennartson A, Roffey A, Moth-Poulsen K. Tetrahedron Lett. 2015; 56: 1457
• 21 Masutani K, Morikawa MA, Kimizuka N. Chem. Commun. (Camb.) 2014; 50: 15803
• 22 Ishiba K, Morikawa MA, Chikara C. , et al. Angew. Chem. Int. Ed. Engl. 2015; 54: 1532
• 23 Duan P, Yanai N, Kimizuka N. J. Am. Chem. Soc. 2013; 135: 19056
• 24 Duan P, Yanai N, Nagatomi H, Kimizuka N. J. Am. Chem. Soc. 2015; 137: 1887
• 25 Hisamitsu S, Yanai N, Kimizuka N. Angew. Chem. Int. Ed. Engl. 2015; 54: 11550
• 26 Ogawa T, Yanai N, Monguzzi A, Kimizuka N. Sci. Rep. 2015; 5: 10882
• 27 Yanai N, Kimizuka N. Chem. Commun. (Camb.) 2016; 52: 5354
• 28 Kimizuka N, Yanai N, Morikawa MA. Langmuir 2016; 32: 12304
• 29 Wohnhaas C, Turshatov A, Mailänder V. , et al. Macromol. Biosci. 2011; 11: 772
• 30 Wohnhaas C, Mailänder V, Dröge M. , et al. Macromol. Biosci. 2013; 13: 1422
• 31 Zhou J, Liu Q, Feng W, Sun Y, Li F. Chem. Rev. 2015; 115: 395
• 32 Liu Q, Yang T, Feng W, Li F. J. Am. Chem. Soc. 2012; 134: 5390
• 33 Kim J-H, Kim J-H. J. Am. Chem. Soc. 2012; 134: 17478
• 34 Turshatov A, Busko D, Baluschev S, Miteva T, Landfester K. New J. Phys. 2011; 13: 083035
• 35 Askes SHC, Bahreman A, Bonnet S. Angew. Chem. Int. Ed. Engl. 2014; 53: 1029
• 36 Askes SHC, López Mora N, Harkes R. , et al. Chem. Commun. (Camb.) 2015; 51: 9137
• 37 Poznik V, Faltermeier V, Dick B, König B. RSC Advances 2016; 6: 41947
• 38 Askes SHC, Brodie P, Bruylants G, Bonnet S. J. Phys. Chem. B 2017; 121: 780
• 39 Kouno H, Ogawa T, Amemori S, Mahato P, Yanai N, Kimizuka N. Chem. Sci. (Camb.) 2016; 7: 5224
• 40 Okahata Y, Kunitake T. J. Am. Chem. Soc. 1979; 101: 5231
• 41 Fuhrhop JH, Wang T. Chem. Rev. 2004; 104: 2901
• 42 Bharmoria P, Hisamitsu S, Nagatomi H. , et al. J. Am. Chem. Soc. 2018; 140: 10848
• 43 Nakashima N, Ando R, Kunitake T. Bull. Chem. Soc. Jpn. 1987; 60: 1967
• 44 Asakuma S, Okada H, Kunitake T. J. Am. Chem. Soc. 1991; 113: 1749
• 45 Kimizuka N, Kawasaki T, Kunitake T. J. Am. Chem. Soc. 1993; 115: 4387
• 46 Kimizuka N, Kawasaki T, Hirata K, Kunitake T. J. Am. Chem. Soc. 1998; 120: 4094
• 47 Synthesis of 2-amino-N1,N5-bis(3-(dodecyloxy)propyl)pentanediamide (1b): Boc-L-Glutamic acid (2.83 g, 11.4 mmol), 3-(dodecyloxy)propylamine (6.2 g, 25.4 mmol) and triethyl amine (4 mL) were taken in a 500 mL round-bottomed flask and dissolved by adding 200 mL of dry dichloromethane (DCM). The mixture was stirred for 15 minutes under an ice bath. Subsequently, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (WSC, 5.51 g, 28.7 mmol) and 1-hydroxybenzotriazole hydrate (HOBt, 4.4 g, 28.7 mmol) were dissolved in 100 mL dry DCM and added dropwise to the cooled reaction mixture. The reaction mixture was stirred for 12 hours under a nitrogen atmosphere with gradual heating to room temperature. Reaction progress was monitored by thin layer chromatography (TLC). When the reaction was complete, the solvent was evaporated and the crude was washed with CHCl₃/water for 3 times. The organic layer was dried over sodium sulfate and filtered. The solvent was evaporated to give a pale-yellow crude which was further purified by column chromatography (Silica, HCl₃/MeOH) to give a colorless solid product (1a, 75% yield). The solid obtained in the first step (1a, 5.8 g, 8.5 mmol) was dissolved in dry DCM (100 mL) and treated with trifluoroacetic acid (TFA, 19 g, 167 mmol). The mixture was stirred overnight at room temperature. After reaction completion, DCM and TFA were evaporated under vacuum to give the product as a yellow oil which upon acidification with 35% HCl (10 g) gave a colorless precipitate. The obtained precipitate was purified by recrystallization from the acetone/methanol solvent mixture (1b, 58% yield). ¹H NMR (CDCl₃, 300 MHz): δ (ppm) = 8.61 (m, 3H, NH₃ ), 8.47 (t, 1H, CO-NH), 7.42 (t, 1H, CO-NH), 4.30 (m, 1H, tert.-CH), 3.51-3.01 (m, 12H), 2.60 (m, 2H), 2.25 (m, 2H), 1.95-1.68 (m, 4H), 1.66-1.02 (m, 40H), 0.90 (t, 6H, CH₃ ). (Figure S1, Supporting Information). Synthesis of 11-((18,22-dioxo-13,27-dioxa-17,23-diazanonatriacontan-19-yl)amino)-N-(2-hydroxyethyl)-N,N-dimethyl-11-oxoundecan-1-aminium (1): The deprotected intermediate product from the previous step (1b, 1.6 g, 2.7 mmol) was taken in 60 mL dry DCM and Et₃N (5 mmol) followed by addition of 11-bromo-undecanoic acid (0.82 g, 3.1 mmol) and DMAP (0.045 g, 0.37 mmol). The reaction mixture was stirred under ice-bath. A WSC (0.6 g, 3.1 mmol) solution in 20 mL dry DCM was added dropwise and stirring was continued for 12 hours at room temperature. After completion of the reaction, the solvent was evaporated, and a residue was washed by CHCl₃/water mixture. The organic phase was dried over sodium sulfate and filtered. The solvent was evaporated under vacuum, and crude was purified by recrystallization from acetone (1c, 78% yield). Finally, intermediate 1c (0.9 g, 1.0 mmol) was reacted with 2-methylaminoethanol (0.5 g, 5.5 mmol) in acetonitrile under reflux condition. The mixture was stirred for 9 hours at 80 °C. The solvent was evaporated to yield white crude which was purified by re-precipitation from MeOH solution by adding CH₃CN (45% yield). ¹H-NMR (CDCl3, 300 MHz): δ (ppm) = δ (ppm) = 7.41 (d, 1H, CO-NH), 7.30 (t, 1H, CO-NH), 6.8 (t, 1H, CO-NH), 4.37 (m, 1H, tert.-CH), 4.1 (m, 2H), 3.73 (m, 2H), 3.22-3.59 (m, 20H), 2.32-2.42 (m, 4H), 1.10-2.10 (m, 64H), 0.88 (t, 6H, CH₃ ). (Figure S2, Supporting Information). MALDI–TOF MS spectrum (dithranol matrix): Calculated molecular weight C₅₀H₁₀₁N₄O₆ ⁺  = 854.36; Obtained = 854.4. Elemental analysis calculated for C₅₀H₁₀₁N₄O₆Br + H₂O: C, 63.06; H, 10.90; Br, 8.39; N, 5.88; O, 11.76. Found: C, 63.34; H, 11.04; N, 5.98
• 48 Nakashima N, Fukushima H, Kunitake T. Chem. Lett. 1981; 10: 1207
• 49 Kawasaki T, Tokuhiro M, Kimizuka N, Kunitake T. J. Am. Chem. Soc. 2001; 123: 6792
• 50 Okazaki Y, Goto T, Sakaguchi R. , et al. Chem. Lett. 2016; 45: 448
• 51 Kumar J, Nakashima T, Kawai T. J. Phys. Chem. Lett. 2015; 6: 3445
• 52 Overton E. Vierteljahrsschr. Naturf. Ges. Zürich 1899; 44: 88
• 53 Widomska J, Raguz M, Subczynski WK. Biochim. Biophys. Acta. 2007; 1768: 2635
• 54 Monguzzi A, Mezyk J, Scotognella F, Tubino R, Meinardi F. Phys. Rev. B Condens. Matter Mater. Phys. 2008; 78: 195112
• 55 Hirata S, Totani K, Zhang J. , et al. Adv. Funct. Mater. 2013; 23: 3386
• 56 An Z, Zheng C, Tao Y. , et al. Nat. Mater. 2015; 14: 685