Phosphorescent rhenium-dipyrrinates

efficient photosensitizers for singlet oxygen generation

Neha Manav, Praseetha E Kesavan, Masatoshi Ishida, Shigeki Mori, Yuhsuke Yasutake, Susumu Fukatsu, Hiroyuki Furuta, Iti Gupta

研究成果: ジャーナルへの寄稿記事

1 引用 (Scopus)

抄録

A series of rhenium(i) dipyrrinato complexes (Re1-Re8) have been prepared and characterized; their crystal structures, phosphorescence and singlet oxygen generation studies are reported. The aromatic substituents, such as thienyl, p-bromophenyl, p-fluorophenyl, m-fluorophenyl, pentaflurophenyl, N-butylcarbazole, N-phenylcarbazole, and N-butylphenothiazine, are linked to the C5 position of Re-dipyrrinates. Varying the electronic nature of the substituents from electron donating (e.g., carbazole) to electron withdrawing (e.g., pentaflurophenyl) allowed the change in the structural, electrochemical, and spectroscopic properties of these complexes. In particular, the rhenium dipyrrinates showed phosphorescence in the near IR region with sufficiently longer triplet state lifetimes (τT = 9-29 μs). Also, a large Stokes shift (Δν = 5682-6957 cm-1) was witnessed for all the rhenium dipyrrinates. Triplet emission was reflected in the efficient singlet oxygen generation yields (ΦΔ ∼ 0.75-0.98) along with the distinct photo-stability. Density functional theory (DFT) calculations revealed that the electron density is spread over the dipyrrin unit in most complexes. Rhenium dipyrrinate having a phenothiazine substituent exhibited the smallest HOMO-LUMO band gap (2.820 eV) among all Re-complexes.

元の言語英語
ページ(範囲)2467-2478
ページ数12
ジャーナルDalton Transactions
48
発行部数7
DOI
出版物ステータス出版済み - 2 12 2019

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Rhenium
Singlet Oxygen
Photosensitizing Agents
Phosphorescence
Electrons
Density functional theory
Carrier concentration
Energy gap
Crystal structure

これを引用

Manav, N., Kesavan, P. E., Ishida, M., Mori, S., Yasutake, Y., Fukatsu, S., ... Gupta, I. (2019). Phosphorescent rhenium-dipyrrinates: efficient photosensitizers for singlet oxygen generation. Dalton Transactions, 48(7), 2467-2478. https://doi.org/10.1039/c8dt04540b

Phosphorescent rhenium-dipyrrinates : efficient photosensitizers for singlet oxygen generation. / Manav, Neha; Kesavan, Praseetha E; Ishida, Masatoshi; Mori, Shigeki; Yasutake, Yuhsuke; Fukatsu, Susumu; Furuta, Hiroyuki; Gupta, Iti.

:: Dalton Transactions, 巻 48, 番号 7, 12.02.2019, p. 2467-2478.

研究成果: ジャーナルへの寄稿記事

Manav, N, Kesavan, PE, Ishida, M, Mori, S, Yasutake, Y, Fukatsu, S, Furuta, H & Gupta, I 2019, 'Phosphorescent rhenium-dipyrrinates: efficient photosensitizers for singlet oxygen generation', Dalton Transactions, 巻. 48, 番号 7, pp. 2467-2478. https://doi.org/10.1039/c8dt04540b
Manav, Neha ; Kesavan, Praseetha E ; Ishida, Masatoshi ; Mori, Shigeki ; Yasutake, Yuhsuke ; Fukatsu, Susumu ; Furuta, Hiroyuki ; Gupta, Iti. / Phosphorescent rhenium-dipyrrinates : efficient photosensitizers for singlet oxygen generation. :: Dalton Transactions. 2019 ; 巻 48, 番号 7. pp. 2467-2478.
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abstract = "A series of rhenium(i) dipyrrinato complexes (Re1-Re8) have been prepared and characterized; their crystal structures, phosphorescence and singlet oxygen generation studies are reported. The aromatic substituents, such as thienyl, p-bromophenyl, p-fluorophenyl, m-fluorophenyl, pentaflurophenyl, N-butylcarbazole, N-phenylcarbazole, and N-butylphenothiazine, are linked to the C5 position of Re-dipyrrinates. Varying the electronic nature of the substituents from electron donating (e.g., carbazole) to electron withdrawing (e.g., pentaflurophenyl) allowed the change in the structural, electrochemical, and spectroscopic properties of these complexes. In particular, the rhenium dipyrrinates showed phosphorescence in the near IR region with sufficiently longer triplet state lifetimes (τT = 9-29 μs). Also, a large Stokes shift (Δν = 5682-6957 cm-1) was witnessed for all the rhenium dipyrrinates. Triplet emission was reflected in the efficient singlet oxygen generation yields (ΦΔ ∼ 0.75-0.98) along with the distinct photo-stability. Density functional theory (DFT) calculations revealed that the electron density is spread over the dipyrrin unit in most complexes. Rhenium dipyrrinate having a phenothiazine substituent exhibited the smallest HOMO-LUMO band gap (2.820 eV) among all Re-complexes.",
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AU - Manav, Neha

AU - Kesavan, Praseetha E

AU - Ishida, Masatoshi

AU - Mori, Shigeki

AU - Yasutake, Yuhsuke

AU - Fukatsu, Susumu

AU - Furuta, Hiroyuki

AU - Gupta, Iti

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N2 - A series of rhenium(i) dipyrrinato complexes (Re1-Re8) have been prepared and characterized; their crystal structures, phosphorescence and singlet oxygen generation studies are reported. The aromatic substituents, such as thienyl, p-bromophenyl, p-fluorophenyl, m-fluorophenyl, pentaflurophenyl, N-butylcarbazole, N-phenylcarbazole, and N-butylphenothiazine, are linked to the C5 position of Re-dipyrrinates. Varying the electronic nature of the substituents from electron donating (e.g., carbazole) to electron withdrawing (e.g., pentaflurophenyl) allowed the change in the structural, electrochemical, and spectroscopic properties of these complexes. In particular, the rhenium dipyrrinates showed phosphorescence in the near IR region with sufficiently longer triplet state lifetimes (τT = 9-29 μs). Also, a large Stokes shift (Δν = 5682-6957 cm-1) was witnessed for all the rhenium dipyrrinates. Triplet emission was reflected in the efficient singlet oxygen generation yields (ΦΔ ∼ 0.75-0.98) along with the distinct photo-stability. Density functional theory (DFT) calculations revealed that the electron density is spread over the dipyrrin unit in most complexes. Rhenium dipyrrinate having a phenothiazine substituent exhibited the smallest HOMO-LUMO band gap (2.820 eV) among all Re-complexes.

AB - A series of rhenium(i) dipyrrinato complexes (Re1-Re8) have been prepared and characterized; their crystal structures, phosphorescence and singlet oxygen generation studies are reported. The aromatic substituents, such as thienyl, p-bromophenyl, p-fluorophenyl, m-fluorophenyl, pentaflurophenyl, N-butylcarbazole, N-phenylcarbazole, and N-butylphenothiazine, are linked to the C5 position of Re-dipyrrinates. Varying the electronic nature of the substituents from electron donating (e.g., carbazole) to electron withdrawing (e.g., pentaflurophenyl) allowed the change in the structural, electrochemical, and spectroscopic properties of these complexes. In particular, the rhenium dipyrrinates showed phosphorescence in the near IR region with sufficiently longer triplet state lifetimes (τT = 9-29 μs). Also, a large Stokes shift (Δν = 5682-6957 cm-1) was witnessed for all the rhenium dipyrrinates. Triplet emission was reflected in the efficient singlet oxygen generation yields (ΦΔ ∼ 0.75-0.98) along with the distinct photo-stability. Density functional theory (DFT) calculations revealed that the electron density is spread over the dipyrrin unit in most complexes. Rhenium dipyrrinate having a phenothiazine substituent exhibited the smallest HOMO-LUMO band gap (2.820 eV) among all Re-complexes.

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