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

doi:10.1038/s41467-022-31164-z

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

Nat Commun. 2022 Jul 5;13(1):3660. doi: 10.1038/s41467-022-31164-z.

Authors

Pedro Paulo Ferreira da Rosa¹, Yuichi Kitagawa^{2

3}, Sunao Shoji^{2

3}, Hironaga Oyama⁴, Keisuke Imaeda⁵, Naofumi Nakayama⁶, Koji Fushimi², Hidehiro Uekusa⁴, Kosei Ueno⁵, Hitoshi Goto⁷, Yasuchika Hasegawa^{8

9}

Affiliations

¹ Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, Hokkaido, 060-8628, Japan.
² Faculty of Engineering, Hokkaido University, Sapporo, Hokkaido, 060-8628, Japan.
³ Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo, Hokkaido, 001-0021, Japan.
⁴ School of Science, Tokyo Institute of Technology, Tokyo, 152-8551, Japan.
⁵ Faculty of Science, Hokkaido University, Sapporo, Hokkaido, 060-0810, Japan.
⁶ CONFLEX Corporation, Tokyo, 108-0074, Japan.
⁷ Information and Media Center, Toyohashi University of Technology, Toyohashi, Aichi, 441-8580, Japan.
⁸ Faculty of Engineering, Hokkaido University, Sapporo, Hokkaido, 060-8628, Japan. hasegaway@eng.hokudai.ac.jp.
⁹ Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo, Hokkaido, 001-0021, Japan. hasegaway@eng.hokudai.ac.jp.

Abstract

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.