A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties

Guochen Bao; Ka-Leung Wong; Dayong Jin; Peter A. Tanner

doi:10.1038/s41377-018-0097-7

Go to Nature Website

Your Location：

Home >

Browse articles >

A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties

Original Articles

- A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties
- Light: Science & Applications Vol. 7, Issue 6, Pages: 915-924(2018)
- Affiliations：
  
  1.Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR, People's Republic of China
  2.Institute for Biomedical Materials and Devices (IBMD), Faculty of Science, University of Technology Sydney, Sydney, NSW, 2007, Australia
  3.School of Mathematical and Physical Sciences, Faculty of Science, University of Technology Sydney, Sydney, NSW, 2007, Australia
- Author bio：
  
  Ka-Leung Wong (klwong@hkbu.edu.hk)
  Dayong Jin(Dayong.Jin@uts.edu.au)
  Peter A. Tanner (peter.a.tanner@gmail.com)
- Funds：
- DOI：10.1038/s41377-018-0097-7
  CLC：
Scan for full text
Bao, G. C. et al. A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties. Light: Science & Applications, 6, 915-924 (2018).
DOI：

Bao, G. C. et al. A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties. Light: Science & Applications, 6, 915-924 (2018). DOI： 10.1038/s41377-018-0097-7.

摘要

Abstract

The optical thermometer has shown great promise for use in the fields of aeronautical engineering, environmental monitoring and medical diagnosis. Self-referencing lanthanide thermo-probes distinguish themselves because of their accuracy, calibration, photostability, and temporal dimension of signal. However, the use of conventional lanthanide-doped materials is limited by their poor reproducibility, random distance between energy transfer pairs and interference by energy migration, thereby restricting their utility. Herein, a strategy for synthesizing hetero-dinuclear complexes that comprise chemically similar lanthanides is introduced in which a pair of thermosensitive dinuclear complexes, cycTb-phEu and cycEu-phTb, were synthesized. Their structures were geometrically optimized with an internuclear distance of approximately 10.6Å. The sensitive linear temperature-dependent luminescent intensity ratios of europium and terbium emission over a wide temperature range (50-298K and 10-200K, respectively) and their temporal dimension responses indicate that both dinuclear complexes can act as excellent self-referencing thermometers. The energy transfer from Tb,3+, to Eu,3+, is thermally activated, with the most important pathway involving the ,7,F,1, Eu,3+,J,-multiplet at room temperature. The energy transfer from the antenna to Eu,3+, was simulated, and it was found that the most important ligand contributions to the rate come from transfers to the Eu,3+, upper states rather than direct ligand-metal transfer to ,5,D,1, or ,5,D,0,. As the first molecular-based thermometer with clear validation of the metal ratio and a fixed distance between the metal pairs, these dinuclear complexes can be used as new materials for temperature sensing and can provide a new platform for understanding the energy transfer between lanthanide ions.

关键词

Keywords

references

Miyata, K. et al. Chameleon luminophore for sensing temperatures: control of metal-to-metal and energy back transfer in lanthanide coordination polymers. Angew. Chem. Int Ed. 52, 6413-6416 (2013).

Hatanaka, M. et al. Organic linkers control the thermosensitivity of the emission intensities from Tb(Ⅲ) and Eu(Ⅲ) in a chameleon polymer. Chem. Sci. 8, 423-429 (2017).

Nakano, M. et al. Genetically encoded ratiometric fluorescent thermometer with wide range and rapid response.PLoS ONE 12, e0172344 (2017).

Wang, X. D., Wolfbeis, O. S. & Meier, R. J. Luminescent probes and sensors for temperature. Chem. Soc. Rev. 42, 7834-7869 (2013).

Cui, Y. J. et al. A luminescent mixed-lanthanide metal-organic framework thermometer. J. Am. Chem. Soc. 134, 3979-3982 (2012).

Marciniak, L., Prorok, K., Francés-Soriano, L., Pérez-Prieto, J. & Bednarkiewicz, A. A broadening temperature sensitivity range with a core-shell YbEr@YbNd double ratiometric optical nanothermometer. Nanoscale 8, 5037-5042 (2016).

N'Dala-Louika, I. et al. Ratiometric mixed Eu-Tb metal-organic framework as a new cryogenic luminescent thermometer. J. Mater. Chem. C. 5, 10933-10937 (2017).

Lu, H. Y. et al. Stark sublevels of Er3+-Yb3+ codoped Gd2(WO4)3 phosphor for enhancing the sensitivity of a luminescent thermometer. RSC Adv. 6, 57667-57671 (2016).

Wang, H. Z., Zhao, D., Cui, Y. J., Yang, Y. & Qian, G. D. A Eu/Tb-mixed MOF for luminescent high-temperature sensing.J. Solid State Chem. 246, 341-345 (2017).

Zhou, J., Xia, Z. G., Bettinelli, M. & Liu, Q. L. Photoluminescence tuning via energy transfer in Eu-doped Ba 2(Gd, Tb)2Si4O13 solid-solution phosphors. RSC Adv. 6, 2046-2054 (2016).

Morrison, G., Latshaw, A. M., Spagnuolo, N. R. & Zur Loye, H. C. Observation of intense X-ray scintillation in a family of mixed anion silicates, Cs 3RESi4O10F2 (RE = Y, Eu-Lu), obtained via an enhanced flux crystal growth technique. J. Am. Chem. Soc. 139, 14743-14748 (2017).

Romanova, K. A., Freidzon, A. Y., Bagaturyants, A. A. & Galyametdinov, Y. G. Ab initio study of energy transfer pathways in dinuclear lanthanide complex of europium(Ⅲ) and terbium(Ⅲ) ions. J. Phys. Chem. A 118, 11244-11252 (2014).

Bao, G. C. et al. Reversible and sensitive Hg2+ detection by a cell-permeable ytterbium complex. Inorg. Chem. 57, 120-128 (2018).

Yu, Y. L. et al. Self-calibrating optic thermometer based on dual-emission nanocomposite. J. Alloy. Compd. 730, 12-16 (2018).

Dai, Z. C. et al. Ratiometric time-gated luminescence probe for hydrogen sulfide based on lanthanide complexes. Anal. Chem. 86, 11883-11889 (2014).

Yang, J., Zhang, C. M., Li, C. X., Yu, Y. N. & Lin, J. Energy transfer and tunable luminescence properties of Eu 3+ in TbBO3 microspheres via a facile hydrothermal process. Inorg. Chem. 47, 7262-7270 (2018).

Rao, X. T. et al. A highly sensitive mixed lanthanide metal-organic framework self-calibrated luminescent thermometer.J. Am. Chem. Soc. 135, 15559-15564 (2013).

Tanaka, F. & Ishibashi, T. Energy transfer between lanthanide ions in dinuclear complexes. J. Chem. Soc., Faraday Trans. 92, 1105-1110 (1996).

Zhong, Q. et al. Novel stoichiometrically erbium−ytterbium cocrystalline complex exhibiting enhanced near-infrared luminescence. Inorg. Chem. 45, 4537-4543 (2016).

Liu, X., Zhu, J., Ni, H. T., Ma, B. & Liu, L. Luminescent properties of a polymer photoluminescent composite containing the binuclear (Eu, Tb) complex as an emitter. J. Macromol. Sci., Part B 55, 20-32 (2016).

Nonat, A., Liu, T., Jeannin, O., Camerel, F. & Charbonnierè, L. J. Energy transfer in supramolecular heteronuclear lanthanide dimers and application to fluoride sensing in water. Chem. Eur. J. 24, 3784-3792 (2018).

Debroye, E. et al. Controlled synthesis of a novel heteropolymetallic complex with selectively incorporated lanthanide(Ⅲ) ions. Inorg. Chem. 53, 1257-1259 (2014).

Natrajan, L. S., Villaraza, A. J. L., Kenwright, A. M., Faulkner S. Controlled preparation of a heterometallic lanthanide complex containing different lanthanides in symmetrical binding pockets.Chem. Comm. 6020-6022 (2009).http://www.ncbi.nlm.nih.gov/pubmed/19809630

Grimme, S., Brandenburg, J. G., Bannwarth, C. & Hansen, A. Consistent structures and interactions by density functional theory with small atomic orbital basis sets. J. Chem. Phys. 143, 054107 (2015).

Weigend, F. & Ahlrichs, R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: design and assessment of accuracy. Phys. Chem. Chem. Phys. 7, 3297-3305 (2005).

Dolg, M., Stoll, H. & Preuss, H. Energy‐adjusted ab initio pseudopotentials for the rare earth elements. J. Chem. Phys. 90, 1730-1734 (1989).

Neese, F. The ORCA program system. Wiley Interdiscip. Rev: Comput. Mol. Sci. 2, 73-78 (2012).

Stewart, J. J. P. Use of semiempirical methods for detecting anomalies in reported enthalpies of formation of organic compounds. J. Phys. Chem. Ref. Data 33, 713-724 (2004).

Rocha, G. B., Freire, R. O., Simas, A. M. & Stewart, J. J. P. RM1: a reparameterization of AM1 for H, C, N, O, P, S, F, Cl, Br, and I. J. Comput. Chem. 27, 1101-1111 (2006).

Dutra, J. D. L., Bispo, T. D. & Freire, R. O. LUMPAC lanthanide luminescence software: efficient and user friendly. J. Comput. Chem. 35, 772-775 (2014).

Malta, O. L. Mechanisms of non-radiative energy transfer involving lanthanide ions revisited. J. Non-Cryst. Solids 354, 4770-4776 (2008).

Pitchaimani, P., Lo, K. M. & Elango, K. P. Synthesis, spectral characterization, crystal structures of lanthanide(Ⅲ) pyrrolidine dithiocarbamate complexes and their catalytic activity. J. Coord. Chem. 68, 2167-2180 (2015).

Eliseeva, S. V. & Bünzli, J. C. G. Lanthanide luminescence for functional materials and bio-sciences. Chem. Soc. Rev. 39, 189-227 (2010).

Sato, S. et al. Luminescence of fusion materials of polymeric chain-structured lanthanide complexes. Polym. J. 47, 195-200 (2015).

Fomina, I. G. et al. Synthesis and characterization of new heterodinuclear (Eu, Tb) lanthanide pivalates. Polyhedron 50, 297-305 (2013).

Irfanullah, M. & Iftikhar, K. Synthesis and spectroscopic analysis of an extended series of hetero dinuclear complexes containing two different lanthanides in 1:1 stoichiometry. Inorg. Chim. Acta 394, 373-384 (2013).

Anh, T. K. et al. Energy transfer between Tb3+ and Eu3+ in Y2O3 crystals. J. Lumin. 39, 215-221 (1988).http://www.sciencedirect.com/science/article/pii/0022231388900324

Carrasco, I., Piccinelli, F. & Bettinelli, M. Luminescence of Tb-based materials doped with Eu 3+: case studies for energy transfer processes. J. Lumin. 189, 71-77 (2017).

Hou, Z. Y. et al. Electrospinning-derived Tb2(WO4)3: Eu3+ nanowires: energy transfer and tunable luminescence properties. Nanoscale 3, 1568-1574 (2011).

Moran, D. M., May, P. S. & Richardson, F. S. Measurement and analysis of electronic energy transfer between Tb 3+ and Eu3+ ions in Cs2NaY1−x−y TbxEuyCl6. Chem. Phys. 186, 77-103 (1994).

Binnemans, K. Interpretation of europium(Ⅲ) spectra. Coord. Chem. Rev. 295, 1-45 (2015).

Tanner, P. A. & Duan, C. K. Luminescent lanthanide complexes: selection rules and design. Coord. Chem. Rev. 254, 3026-3029 (2010).

Dexter, D. L. A theory of sensitized luminescence in solids.J. Chem. Phys. 21, 836-850 (1953).

Laulicht, I., Meirman, S. & Ehrenberg, B. Fluorescent linewidths and excitation transfer in Eu 0.33Tb0.66P5O14 crystals. J. Lumin. 31-32, 814-816 (1984).http://www.sciencedirect.com/science/article/pii/0022231384901340

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

No data

Related Author

No data

Related Institution

No data

⁰