Ferreira da Rosa Pedro Paulo, Kitagawa Yuichi, Shoji Sunao, Oyama Hironaga, Imaeda Keisuke, Nakayama Naofumi, Fushimi Koji, Uekusa Hidehiro, Ueno Kosei, Goto Hitoshi, Hasegawa Yasuchika
Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, Hokkaido, 060-8628, Japan.
Faculty of Engineering, Hokkaido University, Sapporo, Hokkaido, 060-8628, Japan.
Nat Commun. 2022 Jul 5;13(1):3660. doi: 10.1038/s41467-022-31164-z.
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.
软晶体被定义为具有高度有序结构的柔性分子固体,并且在基于外部触发因素和环境的分子传感材料中受到了关注。在此,我们展示了绿色发光的Tb(III)和黄色发光的Dy(III)配位中心的软晶体共聚。软晶体聚合是通过单体双核配合物和聚合物结构在配位数和几何形状方面的转变来实现的。使用单晶和粉末X射线衍射对结构转变进行了表征。相连的Tb(III)晶体-Dy(III)晶体在蓝光激发下(选择性Dy(III)中心激发:460±10 nm)显示出从Dy(III)中心到Tb(III)中心的光子能量转移。利用与温度相关的发射寿命和发射量子产率以及含时密度泛函理论(B3LYP)计算来估算能量转移的活化能。通过在晶体介质上进行软晶体聚合,成功制备了具有显著长程能量迁移的发光导电聚合物——光子分子链。