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Fast and long-range triplet exciton diffusion in metal–organic frameworks for photon upconversion at ultralow excitation power

Nature Materials volume 14, pages 924–930 (2015)Cite this article

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A Retraction to this article was published on 20 December 2016

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Abstract

The conversion of low-energy light into photons of higher energy based on sensitized triplet–triplet annihilation upconversion (TTA-UC) has emerged as a promising wavelength-shifting methodology because it permits UC at excitation powers as low as the solar irradiance. However, its application has been significantly hampered by the slow diffusion of excited molecules in solid matrices. Here, we introduce metal–organic frameworks (MOFs) that promote TTA-UC by taking advantage of triplet exciton migration among fluorophores that are regularly aligned with spatially controlled chromophore orientations. We synthesized anthracene-containing MOFs with different molecular orientations, and the analysis of TTA-UC emission kinetics unveiled a high triplet diffusion rate with a micrometre-scale diffusion length. Surface modification of MOF nanocrystals with donor molecules and their encapsulation in glassy poly(methyl methacrylate) (PMMA) allowed the construction of molecular-diffusion-free solid-state upconverters, which lead to an unprecedented maximization of overall UC quantum yield at excitation powers comparable to or well below the solar irradiance.

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Figure 1: A schematic representation of TTA-UC by triplet exciton diffusion in MOFs.
Figure 2: Systematic tuning of acceptor arrangements in MOFs.
Figure 3: Observation of photon upconversion in MOFs.
Figure 4: Molecular-diffusion-free solid-state TTA-UC with maximized UC efficiency from very low excitation power.

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Change history

  • 24 November 2016

    We wish to retract this Article due to concerns with some data related to upconversion in the solid-state samples presented in Fig. 4d,e, and to the reproducibility check of the triplet diffusion constant provided in the Supplementary Information. In this Article, we reported fast triplet energy migration and efficient photon upconversion at low excitation intensity in metal–organic frameworks (MOFs). We have since been able to observe the upconverted emission from MOFs both in benzene dispersions and in polymeric films; hence, the concept of photon upconversion in MOFs based on triplet energy migration remains valid. However, we are now unable to observe solid-state upconversion emission at the low excitation intensity reported in Fig. 4d,e, and to quantitatively reproduce the triplet diffusion constants in MOFs reported in Supplementary Figs 8–13 and Supplementary Tables 1–3. Since these are key parameters of this paper, all authors wish to retract this Article. We deeply regret these circumstances and sincerely apologize to the scientific community for the inconvenience this publication has caused to others.

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Acknowledgements

This work was partly supported by a Grants-in-Aid for Scientific Research (S) (25220805), a Grants-in-Aid for Young Scientists (B) (26810036), a Grant-in-Aid for Scientific Research on Innovative Area (26104529) from the Ministry of Education, Culture Sports, Science and Technology of Japan, the JSPS-NSF International Collaborations in Chemistry (ICC) program, and a research grant from The Noguchi Institute. P.M. and A.M. acknowledge JSPS postdoctoral fellowships for foreign researchers. The authors acknowledge M.-a. Morikawa and R. Yoshida in Kyushu University for their help in TEM measurements.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Graduate School of Engineering, Center for Molecular Systems (CMS), Kyushu University, Fukuoka-819-0395, Japan

    Prasenjit Mahato, Nobuhiro Yanai, Teppei Yamada & Nobuo Kimizuka

  2. Dipartimento di Scienza dei Materiali, Università degli Studi Milano-Bicocca, Via Roberto Cozzi 55 20135 Milano, Italy,

    Angelo Monguzzi

  3. PRESTO, JST, Honcho 4-1-8, Kawaguchi, Saitama 332-0012, Japan

    Nobuhiro Yanai & Teppei Yamada

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Contributions

N.Y. and N.K. conceived and designed the project; P.M., A.M. and N.Y. performed the experiments and analysed the data; T.Y. assisted in the crystallographic study; P.M., A.M., N.Y. and N.K. co-wrote the paper.

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Correspondence to Nobuhiro Yanai or Nobuo Kimizuka.

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Mahato, P., Monguzzi, A., Yanai, N. et al. Fast and long-range triplet exciton diffusion in metal–organic frameworks for photon upconversion at ultralow excitation power. Nature Mater 14, 924–930 (2015). https://doi.org/10.1038/nmat4366

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