Photon Upconversion in Supramolecular Gel Matrixes: Spontaneous Accumulation of Light-Harvesting Donor-Acceptor Arrays in Nanofibers and Acquired Air Stability

被引:265
作者
Duan, Pengfei [1 ]
Yanai, Nobuhiro [1 ,2 ]
Nagatomi, Hisanori [1 ]
Kimizuka, Nobuo [1 ]
机构
[1] Kyushu Univ, Grad Sch Engn, Ctr Mol Syst, Dept Chem & Biochem,Nishi Ku, Fukuoka 8190395, Japan
[2] JST, PRESTO, Kawaguchi, Saitama 3320012, Japan
关键词
TRIPLET-TRIPLET ANNIHILATION; LOW-POWER; CHIROPTICAL SWITCH; MOLECULAR DESIGN; ORGANOGELS; LIQUIDS; ORGANIZATION; DERIVATIVES; CHIRALITY; EMISSION;
D O I
10.1021/ja511061h
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Efficient triple-ttriplet annihilation (TTA)-based photon upconversion (UC) is achieved in supramolecular organogel matrixes. Intense UC emission was observed from donor (sensitizer)acceptor (emitter) pairs in organogels even under air-saturated condition, which solved a major problem: deactivation of excited triplet states and TTA-UC by molecular oxygen. These unique TTA-UC molecular systems were formed by spontaneous accumulation of donor and acceptor molecules in the gel nanofibers which are stabilized by developed hydrogen bond networks. These molecules preorganized in nanofibers showed efficient transfer and migration of triplet energy, as revealed by a series of spectroscopic, microscopic, and rheological characterizations. Surprisingly, the donor and acceptor molecules incorporated in nanofibers are significantly protected from the quenching action of dissolved molecular oxygen, indicating very low solubility of oxygen to nanofibers. In addition, efficient TTA-UC is achieved even under excitation power lower than the solar irradiance. These observations clearly unveil the adaptive feature of host gel nanofiber networks that allows efficient and cooperative inclusion of donoracceptor molecules while maintaining their structural integrity. As evidence, thermally induced reversible assembly/disassembly of supramolecular gel networks lead to reversible modulation of the UC emission intensity. Moreover, the air-stable TTA-UC in supramolecular gel nanofibers was generally observed for a wide combination of donoracceptor pairs which enabled near IR-to-yellow, red-to-cyan, green-to-blue, and blue-to-UV wavelength conversions. These findings provide a new perspective of air-stable TTA-UC molecular systems; spontaneous and adaptive accumulation of donor and acceptor molecules in oxygen-blocking, self-assembled nanomatrixes. The oxygen-barrier property of l-glutamate-derived organogel nanofibers has been unveiled for the first time, which could find many applications in stabilizing air-sensitive species in aerated systems.
引用
收藏
页码:1887 / 1894
页数:8
相关论文
共 61 条
[1]   Organogels as scaffolds for excitation energy transfer and light harvesting [J].
Ajayaghosh, Ayyappanpillai ;
Praveen, Vakayil K. ;
Vijayakumar, Chakkooth .
CHEMICAL SOCIETY REVIEWS, 2008, 37 (01) :109-122
[2]  
[Anonymous], AMINO ACIDS
[3]   Activation of a Photodissociative Ruthenium Complex by Triplet-Triplet Annihilation Upconversion in Liposomes [J].
Askes, Sven H. C. ;
Bahreman, Azadeh ;
Bonnet, Sylvestre .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (04) :1029-1033
[4]   A general approach for non-coherently excited annihilation up-conversion: transforming the solar-spectrum [J].
Baluschev, S. ;
Yakutkin, V. ;
Miteva, T. ;
Wegner, G. ;
Roberts, T. ;
Nelles, G. ;
Yasuda, A. ;
Chernov, S. ;
Aleshchenkov, S. ;
Cheprakov, A. .
NEW JOURNAL OF PHYSICS, 2008, 10
[5]   Up-conversion fluorescence: Noncoherent excitation by sunlight [J].
Baluschev, S. ;
Miteva, T. ;
Yakutkin, V. ;
Nelles, G. ;
Yasuda, A. ;
Wegner, G. .
PHYSICAL REVIEW LETTERS, 2006, 97 (14)
[6]   Ultrabright oxygen optodes based on cyclometalated lridium(III) coumarin complexes [J].
Borisov, Sergey M. ;
Klimant, Ingo .
ANALYTICAL CHEMISTRY, 2007, 79 (19) :7501-7509
[7]   Host-guest antenna materials [J].
Calzaferri, G ;
Huber, S ;
Maas, H ;
Minkowski, C .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (32) :3732-3758
[8]   On the efficiency limit of triplet-triplet annihilation for photochemical upconversion [J].
Cheng, Yuen Yap ;
Khoury, Tony ;
Clady, Raphael G. C. R. ;
Tayebjee, Murad J. Y. ;
Ekins-Daukes, N. J. ;
Crossley, Maxwell J. ;
Schmidt, Timothy W. .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2010, 12 (01) :66-71
[9]   Bioinspired molecular design of light-harvesting multiporphyrin arrays [J].
Choi, MS ;
Yamazaki, T ;
Yamazaki, I ;
Aida, T .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (02) :150-158
[10]   What Kind of "Soft Materials" Can We Design from Molecular Gels? [J].
Dawn, Arnab ;
Shiraki, Tomohiro ;
Haraguchi, Shuichi ;
Tamaru, Shun-ichi ;
Shinkai, Seiji .
CHEMISTRY-AN ASIAN JOURNAL, 2011, 6 (02) :266-282