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Wavelength of Luminescence and Energy Level Structure of Binuclear Copper(I) Complex

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The DV-Xα Molecular-Orbital Calculation Method

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Abstract

We investigate the mechanism of strong fluorescence and phosphorescence observed in the binuclear copper complexes by means of a discrete variational (DV)-Xα molecular orbital calculation. Comparing to the energy differences among a occupied and unoccupied molecular orbitals, we can reveal the photon energy of the light of the luminescence in a quantitative way. We also obtained the strong relationship between the observed and the calculated photon energies with according to the conservation of energy principle.

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Acknowledgement

The authors express their thanks to Drs. F. Izumi and K. Momma (Nat’l Inst. for Materials Sci., Japan) for permission to use the 3D visualization program “VESTA”. The authors express their gratitude to Prof. H. Adachi (Kyoto Univ.) for permission to use his computational program. The authors also thank Drs. R. Sekine (Shizuoka Univ.), Y. Kowada (Hyogo Univ. of Teacher Edu.), and M. Mizuno (Osaka Univ.) for fruitful discussions and useful technical advice. The authors also thank to Profs. K. Toriumi and Y. Ozawa (Univ. of Hyogo) for fruitful discussions about the molecular structure in the excited state.

Author information

Authors and Affiliations

  1. Department of Advanced Materials Science, Faculty of Engineering, Kagawa University, 2217-20 Hayashicho, Takamatsu, 761-0396, Kagawa, Japan

    Tomohiko Ishii & Masahiro Kenmotsu

  2. Department of Chemistry, Faculty of Science, University of Toyama, Gofuku 3190, Toyama-shi, 930-8555, Toyama, Japan

    Kiyoshi Tsuge

  3. Department of Chemistry, Faculty of Science, Okayama University of Science, 1-1, Ridaicho, 700-0005, Okayama, Japan

    Genta Sakane

  4. Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo, 060-0810, Hokkaido, Japan

    Yoichi Sasaki

  5. Department of Chemistry, Graduate School of Science, Tohoku University, Aoba, Aramaki, Aoba-ku, Sendai, 980-8578, Miyagi, Japan

    Masahiro Yamashita & Brian K. Breedlove

Authors
  1. Tomohiko Ishii
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  2. Masahiro Kenmotsu
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  3. Kiyoshi Tsuge
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  4. Genta Sakane
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  5. Yoichi Sasaki
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  6. Masahiro Yamashita
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  7. Brian K. Breedlove
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Corresponding author

Correspondence to Tomohiko Ishii .

Editor information

Editors and Affiliations

  1. Faculty of Engineering Dept. of Advanced Materials Science, Kagawa University, Takamatsu, Japan

    Tomohiko Ishii

  2. Faculty of Science, Fukuoka University, Johnan-ku, Fukuoka, Japan

    Hisanobu Wakita

  3. Department of Chemistry, Kwansei Gakuin University, Hyogo, Japan

    Kazuyoshi Ogasawara

  4. Korea Basic Science Institute, Suncheon, Korea, Republic of (South Korea)

    Yang-Soo Kim

Electronic Supporting Information (ESI)

Electronic Supporting Information (ESI)

Fig. 14.19
figure 19

Expected molecular structural deformation of Cu2(μ-Br)2(PPh3)2L2 after irradiating with an ultraviolet light (model 5)

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Fig. 14.20
figure 20

Ligand (L) dependence of the energy level structures of L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L = dmap, 3-bzpy, bpy, 1,5-nap, 1,6-nap, quina, 4-bzpy, and pyz) (model 1). Solid and dashed lines denote the occupied and the unoccupied molecular orbitals, respectively. The colors used in this figure correspond to the observed luminescence wavelengths

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Fig. 14.21
figure 21

Partial density of states (p-DOS) near the Fermi energy level of L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L-M-L) (model 1) (top) and L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L-M-L-M-L) (model 2) (bottom) (L = bpy)

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Fig. 14.22
figure 22

Partial density of states (p-DOS) near the Fermi energy level of L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L-M-L) (model 1) (top) and L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L-M-L-M-L) (model 2) (bottom) (L = quina)

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Fig. 14.23
figure 23

Partial density of states (p-DOS) near the Fermi energy level of L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L-M-L) (model 1) (top) and L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L-M-L-M-L) (model 2) (bottom) (L = 1,6-nap)

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Fig. 14.24
figure 24

Partial density of states (p-DOS) near the Fermi energy level of L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L-M-L) (model 1) (top) and L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L-M-L-M-L) (model 2) (bottom) (L = 1,5-nap)

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Fig. 14.25
figure 25

Partial density of states (p-DOS) near the Fermi energy level after 0, 2, 5, and 10 % structural deformation of L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L-M-L) (model 1) (L = 1,5-nap)

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Fig. 14.26
figure 26

Partial density of states (p-DOS) near the Fermi energy level after 0, 2, 5, and 10 % structural deformation of L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L-M-L) (model 1) (L = bpy)

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Fig. 14.27
figure 27

Partial density of states (p-DOS) near the Fermi energy level after 0, 2, 5, and 10 % structural deformation of L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L-M-L) (model 1) (L = 3-bzpy)

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Fig. 14.28
figure 28

Partial density of states (p-DOS) near the Fermi energy level of L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L-M-L) (model 1) (top), Cu(μ-Br)2Cu-L-Cu(μ-Br)2Cu (model 3) (middle), and CuBr2-L-CuBr2 (model 4) (bottom) (L = quina)

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Fig. 14.29
figure 29

Partial density of states (p-DOS) near the Fermi energy level of L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L-M-L) (model 1) (top), Cu(μ-Br)2Cu-L-Cu(μ-Br)2Cu (model 3) (middle), and CuBr2-L-CuBr2 (model 4) (bottom) (L = 1,6-nap)

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Fig. 14.30
figure 30

Partial density of states (p-DOS) near the Fermi energy level of L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L-M-L) (model 1) (top), Cu(μ-Br)2Cu-L-Cu(μ-Br)2Cu (model 3) (middle), and CuBr2-L-CuBr2 (model 4) (bottom) (L = 1,5-nap)

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Fig. 14.31
figure 31

Partial density of states (p-DOS) near the Fermi energy level of L-Cu(PPh3)(μ-Br)2Cu(PPh3)-L (L-M-L) (model 1) (top), Cu(μ-Br)2Cu-L-Cu(μ-Br)2Cu (model 3) (middle), and CuBr2-L-CuBr2 (model 4) (bottom) (L = bpy)

Full size image

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Ishii, T. et al. (2015). Wavelength of Luminescence and Energy Level Structure of Binuclear Copper(I) Complex. In: Ishii, T., Wakita, H., Ogasawara, K., Kim, YS. (eds) The DV-Xα Molecular-Orbital Calculation Method. Springer, Cham. https://doi.org/10.1007/978-3-319-11185-8_14

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