4.8 Article

Preparation of photonic molecular trains via soft-crystal polymerization of lanthanide complexes

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NATURE COMMUNICATIONS
卷 13, 期 1, 页码 -

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NATURE PORTFOLIO
DOI: 10.1038/s41467-022-31164-z

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  1. Japan Society for the Promotion of Science (JSPS) KAKENHI of the Ministry of Education, Culture, Sports, Science, and Technology (MEXT) of Japan [JP18H04504, JP20H04661, JP18H02041, JP20H04653, JP20H05197, JP20K21201, JP19H04556, JP20H02748, JP17H06373, JP21K05105]
  2. Institute for Chemical Reaction Design and Discovery (ICReDD)
  3. JSPS of MEXT, Japan [19J20713]

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Soft-crystal copolymerization of Tb(III) and Dy(III) complexes is achieved, and long-range energy transfer from one crystal to the other is studied.
Soft-crystals are defined as flexible molecular solids with highly ordered structures and have attracted attention in molecular sensing materials based on external triggers and environments. Here, we show the soft-crystal copolymerization of green-luminescent Tb(III) and yellow-luminescent Dy(III) coordination centers. Soft-crystal polymerization is achieved via transformation of monomeric dinuclear complexes and polymeric structures with respect to coordination number and geometry. The structural transformation is characterized using single-crystal and powder X-ray diffraction. The connected Tb(III) crystal-Dy(III) crystal show photon energy transfer from the Dy(III) centre to the Tb(III) centre under blue light excitation (selective Dy(III) centre excitation: 460 +/- 10 nm). The activation energy of the energy transfer is estimated using the temperature-dependent emission lifetimes and emission quantum yields, and time-dependent density functional theory (B3LYP) calculations. Luminescence-conductive polymers, photonic molecular trains, are successfully prepared via soft-crystal polymerization on crystal media with remarkable long-range energy migration. Soft-crystals are molecular solids with highly ordered structures. Here, authors report the soft-crystal copolymerization of green-luminescent Tb(III) and yellow-luminescent Dy(III) complexes, and study the long-range energy transfer from one crystal to the other.

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