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Aspects of lanthanide complexes for selectivity, intensity and sharpness in luminescence bands from twenty-four praseodymium, europium and gadolinium complexes with differently distorted-hexadentate ligands

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Abstract

We structurally and spectroscopically investigated a series of praseodymium (Pr) complexes with eight ligands that form helicate molecular structures. The mother ligand skeleton (L) has two bipyridine moieties bridged with ethylenediamine. The bridged skeleton of PrL was changed to diamines 1–methyl-ethy-lenediamine, trimethylenediamine and 2,2’-dimethyl-trimethylenediamine, and the corresponding ligands were designated as Lme, Lpr and Ldmpr, for each Pr in these complexes upon UV-excitation. The luminescence quantum yields of PrL and PrLpr in the visible and near infrared (NIR) regions indicate that PrL is excited by both the electronic state of the ligand and the ff absorption band, whereas PrLpr is excited through the ligand. The addition of a methyl group to PrL and PrLpr has a different effect on the Pr emission intensity with the intensity of PrLme decreasing more than that of PrL and prLdmpr and increasing more than that of PrLpr. Thus, the coordination of Pr and the increased rigidity of the ligand upon methyl-ation enhance luminescence. The azomethine moieties on Lme, Lpr and Ldmpr were reduced and formed the corresponding PrLH, PrLmeH, PrLprH and prLdmprH complexes. The luminescence of the non-methylated series is due to transitions related to the 1D2 level and thus the methylated series luminesces due to high energy levels such as 3PJ arising from the shortened π electronic systems. We also discuss the strong red emission of a series of Eu complexes with eight ligands from the viewpoint of their molecular structures and luminescence efficiencies and evaluate the Judd-Ofelt parameters from the luminescence spectra of Eu complexes.

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Authors and Affiliations

  1. Department of Chemistry and Biological Science, College of Science and Engineering, Aoyama Gakuin University, 5–10–1 Fuchinobe, 252-5258, Chuo-ku, Sagamihara, Kanagawa, Japan

    Miki Hasegawa, Shoya Sakurai, Masafumi Andrew Yamaguchi, Daichi Iwasawa, Naho Yajima, Shuhei Ogata & Yudai Inazuka

  2. Mirai Molecular Materials Design Institute, Aoyama Gakuin University, 5–10–1 Fuchinobe, 252-5258, Chuo-ku, Sagamihara, Kanagawa, Japan

    Miki Hasegawa & Ayumi Ishii

  3. JST, PRESTO, 4–1–8 Moncho, 332-0012, Kawaguchi, Saitama, Japan

    Ayumi Ishii

  4. Graduate School of Engineering, Toin University of Yokohama, 225-8503, Kurogane-cho, Aoba-ku, Yokohama, Kanagawa, Japan

    Ayumi Ishii

  5. Hamamatsu Photonics K. K, 812 Joko-cho, 341-3196, Higashi-ku, Hamamatsu, Shizuoka, Japan

    Kengo Suzuki

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  1. Miki Hasegawa
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  2. Shoya Sakurai
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  3. Masafumi Andrew Yamaguchi
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Correspondence to Miki Hasegawa.

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Dedicated to Professor Emeritus Dr Toshihiko Hoshi on the occasion of his 85th birthday.

Electronic supplementary information (ESI) available: Packing structures of Pr and Eu complexes, excitation spectra, NIR-luminescence spectra, luminescence decay profiles, calculation of energy transfer efficiencies, energy diagram of Pr-luminescencent complexes and 1H NMR of each ligand. CCDC 1017809, 1043544, 1017810, 1043545, 1861234, 1861235 and 1861236. For ESI and crystal-lographic data in CIF or other electronic format see DOI: 10.1039/d0pp00069h

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Hasegawa, M., Sakurai, S., Yamaguchi, M.A. et al. Aspects of lanthanide complexes for selectivity, intensity and sharpness in luminescence bands from twenty-four praseodymium, europium and gadolinium complexes with differently distorted-hexadentate ligands. Photochem Photobiol Sci 19, 1054–1062 (2020). https://doi.org/10.1039/d0pp00069h

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