Polymorphism-based luminescence of lanthanide complexes with a deuterated 1,10-phenanthroline

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• 作者：S. Ogata ; A. Ishii ; C.L. Lu ; T. Kondo ; N. Yajima ; M. Hasegawa ; ^{hasemiki@chem.aoyama.ac.jp}
• 关键词：Lanthanide complexes ; Phenanthroline ; Polymorphism ; Ff emission ; Energy transfer ; Synchrotron X-ray diffraction
• 刊名：Journal of Photochemistry and Photobiology A: Chemistry
• 出版年：2017
• 出版时间：1 February 2017
• 年：2017
• 卷：334
• 期：Complete
• 页码：55-60
• 全文大小：1341 K
• 卷排序：334

文摘

To clarify the deuteration effect and polymorphism effect on the ff emission of lanthanide complexes, we used phenanthroline and its deuterated one (abbreviated to phen and phen-d8, respectively). Eu, Tb, Gd and Tm ion were used as center metals.. Phen complexes with lanthanide ion form polymorphism such as modification IIa and I. The component ratios of polymorphism of Eu or Tb complexes were estimated by a synchrotron XRD, and depended on the hydrogen atom with/without deuteration on aromatic carbon. In this study, the ratios of polymorphism of Gd or Tm complexes with phen were newly analyzed by a synchrotron XRPD even in tiny amount of mixing compounds.. An explanation with logical consistency was shown to assign the luminescence and polymorphism by luminescence lifetimes and synchrotron XRD. Thus, the luminescence component ratios of lanthanide complexes with phen corresponded to the ratios from the observation of XRD. Furthermore, each luminescence quantum yields of two modification in Eu complexes were able to theoretically estimate from the data of mixed crystals. . Finally, energy diagrams of the ff emission enhanced their deuteration were demonstrated for the Eu, Tb and Tm complexes. Luminescence of Eu was intensified by the deuteration of phen, due to the over tones of CH/D vibrations. Tb had no influence clearly by the deuteration in phen, but did by the polymorphism formation. Blue luminescence of Tm was observed in both phen/phen-d8 complexes..