Preparation of photonic molecular trains via soft-crystal polymerization of lanthanide complexes
Pedro Paulo Ferreira da Rosa, Yuichi Kitagawa, Sunao Shoji, Hironaga Oyama, Keisuke Imaeda, Naofumi Nakayama, Koji Fushimi, Hidehiro Uekusa, Kosei Ueno, Hitoshi Goto & Yasuchika Hasegawa
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.
highly order structure, B3LYP,