2,2′-Bipyridines carrying a diazo moiety and their complexes with bis(hexafluoroacetylacetonato)copper: Synthesis, structures, electronic and magnetic properties of their photoproducts in frozen solutions

H. Morikawa, F. Imamura, Y. Tsurukami, T. Itoh, H. Kumada, Satoru Karasawa, N. Koga, H. Iwamura

研究成果: ジャーナルへの寄稿記事

17 引用 (Scopus)

抄録

4-(α-Diazobenzyl)-2,2′-bipyridine 2, diazodi{4-(2,2′-bipyridyl)}methane 3, and 1,3-benzenediyl{4-(4′-methyl-2.2°prime;-bipyridyl)diazomethane} 4 were prepared as new types of spin sources/magnetic couplers. The molecular structures of bipyridine ligands, 2, 3, 4, and [Cu(hfac)2·2] were revealed by X-ray analyses. Photolysis of 2, 3, 4, and their complexes with Cu(hfac)2 in MTHF frozen solutions at cryogenic temperature was followed by UV-Vis and EPR spectroscopy. UV-Vis and EPR spectra after photolysis showed strong two absorptions; at 508 and 471 nm for 2, and 511 and 476 nm for 3, and characteristic sets of EPR signals due to the triplet states; |D/hc|=0.418, and 0.436 cm-1 and |E/hc|=0.021 and 0.022 cm-1 for 2 and 3, respectively. Diazo compound 4 after photolysis also showed absorptions at 506 and 471 nm and EPR signals characteristic of a quintet. Their complexes with Cu(hfac)2 showed a red shift of 3-14 nm in the visible spectra and gave EPR spectra characteristic of the high-spin complexes under similar conditions. Magnetic susceptibility measurements on a SQUID magnetometer were carried out using a sample similar to the one employed in the UV-Vis and EPR studies. The field dependence of magnetization in frozen solution suggested that the ground-state spin multiplicities of the photoproducts of 2, 3, and 4 were triplet, triplet, and quintet, respectively. Similarly, those of their complexes with Cu(hfac)2 were quartet, quintet, and septet, respectively.

元の言語英語
ページ(範囲)493-502
ページ数10
ジャーナルJournal of Materials Chemistry
11
発行部数2
DOI
出版物ステータス出版済み - 3 15 2001

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Electronic properties
Paramagnetic resonance
Copper
Magnetic properties
Photolysis
2,2'-Dipyridyl
Diazomethane
SQUIDs
Methane
Magnetometers
Magnetic susceptibility
Cryogenics
Ground state
Molecular structure
Magnetization
Ligands
Spectroscopy
X rays
Temperature

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Chemistry

これを引用

2,2′-Bipyridines carrying a diazo moiety and their complexes with bis(hexafluoroacetylacetonato)copper : Synthesis, structures, electronic and magnetic properties of their photoproducts in frozen solutions. / Morikawa, H.; Imamura, F.; Tsurukami, Y.; Itoh, T.; Kumada, H.; Karasawa, Satoru; Koga, N.; Iwamura, H.

:: Journal of Materials Chemistry, 巻 11, 番号 2, 15.03.2001, p. 493-502.

研究成果: ジャーナルへの寄稿記事

Morikawa, H. ; Imamura, F. ; Tsurukami, Y. ; Itoh, T. ; Kumada, H. ; Karasawa, Satoru ; Koga, N. ; Iwamura, H. / 2,2′-Bipyridines carrying a diazo moiety and their complexes with bis(hexafluoroacetylacetonato)copper : Synthesis, structures, electronic and magnetic properties of their photoproducts in frozen solutions. :: Journal of Materials Chemistry. 2001 ; 巻 11, 番号 2. pp. 493-502.
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title = "2,2′-Bipyridines carrying a diazo moiety and their complexes with bis(hexafluoroacetylacetonato)copper: Synthesis, structures, electronic and magnetic properties of their photoproducts in frozen solutions",
abstract = "4-(α-Diazobenzyl)-2,2′-bipyridine 2, diazodi{4-(2,2′-bipyridyl)}methane 3, and 1,3-benzenediyl{4-(4′-methyl-2.2°prime;-bipyridyl)diazomethane} 4 were prepared as new types of spin sources/magnetic couplers. The molecular structures of bipyridine ligands, 2, 3, 4, and [Cu(hfac)2·2] were revealed by X-ray analyses. Photolysis of 2, 3, 4, and their complexes with Cu(hfac)2 in MTHF frozen solutions at cryogenic temperature was followed by UV-Vis and EPR spectroscopy. UV-Vis and EPR spectra after photolysis showed strong two absorptions; at 508 and 471 nm for 2, and 511 and 476 nm for 3, and characteristic sets of EPR signals due to the triplet states; |D/hc|=0.418, and 0.436 cm-1 and |E/hc|=0.021 and 0.022 cm-1 for 2 and 3, respectively. Diazo compound 4 after photolysis also showed absorptions at 506 and 471 nm and EPR signals characteristic of a quintet. Their complexes with Cu(hfac)2 showed a red shift of 3-14 nm in the visible spectra and gave EPR spectra characteristic of the high-spin complexes under similar conditions. Magnetic susceptibility measurements on a SQUID magnetometer were carried out using a sample similar to the one employed in the UV-Vis and EPR studies. The field dependence of magnetization in frozen solution suggested that the ground-state spin multiplicities of the photoproducts of 2, 3, and 4 were triplet, triplet, and quintet, respectively. Similarly, those of their complexes with Cu(hfac)2 were quartet, quintet, and septet, respectively.",
author = "H. Morikawa and F. Imamura and Y. Tsurukami and T. Itoh and H. Kumada and Satoru Karasawa and N. Koga and H. Iwamura",
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T1 - 2,2′-Bipyridines carrying a diazo moiety and their complexes with bis(hexafluoroacetylacetonato)copper

T2 - Synthesis, structures, electronic and magnetic properties of their photoproducts in frozen solutions

AU - Morikawa, H.

AU - Imamura, F.

AU - Tsurukami, Y.

AU - Itoh, T.

AU - Kumada, H.

AU - Karasawa, Satoru

AU - Koga, N.

AU - Iwamura, H.

PY - 2001/3/15

Y1 - 2001/3/15

N2 - 4-(α-Diazobenzyl)-2,2′-bipyridine 2, diazodi{4-(2,2′-bipyridyl)}methane 3, and 1,3-benzenediyl{4-(4′-methyl-2.2°prime;-bipyridyl)diazomethane} 4 were prepared as new types of spin sources/magnetic couplers. The molecular structures of bipyridine ligands, 2, 3, 4, and [Cu(hfac)2·2] were revealed by X-ray analyses. Photolysis of 2, 3, 4, and their complexes with Cu(hfac)2 in MTHF frozen solutions at cryogenic temperature was followed by UV-Vis and EPR spectroscopy. UV-Vis and EPR spectra after photolysis showed strong two absorptions; at 508 and 471 nm for 2, and 511 and 476 nm for 3, and characteristic sets of EPR signals due to the triplet states; |D/hc|=0.418, and 0.436 cm-1 and |E/hc|=0.021 and 0.022 cm-1 for 2 and 3, respectively. Diazo compound 4 after photolysis also showed absorptions at 506 and 471 nm and EPR signals characteristic of a quintet. Their complexes with Cu(hfac)2 showed a red shift of 3-14 nm in the visible spectra and gave EPR spectra characteristic of the high-spin complexes under similar conditions. Magnetic susceptibility measurements on a SQUID magnetometer were carried out using a sample similar to the one employed in the UV-Vis and EPR studies. The field dependence of magnetization in frozen solution suggested that the ground-state spin multiplicities of the photoproducts of 2, 3, and 4 were triplet, triplet, and quintet, respectively. Similarly, those of their complexes with Cu(hfac)2 were quartet, quintet, and septet, respectively.

AB - 4-(α-Diazobenzyl)-2,2′-bipyridine 2, diazodi{4-(2,2′-bipyridyl)}methane 3, and 1,3-benzenediyl{4-(4′-methyl-2.2°prime;-bipyridyl)diazomethane} 4 were prepared as new types of spin sources/magnetic couplers. The molecular structures of bipyridine ligands, 2, 3, 4, and [Cu(hfac)2·2] were revealed by X-ray analyses. Photolysis of 2, 3, 4, and their complexes with Cu(hfac)2 in MTHF frozen solutions at cryogenic temperature was followed by UV-Vis and EPR spectroscopy. UV-Vis and EPR spectra after photolysis showed strong two absorptions; at 508 and 471 nm for 2, and 511 and 476 nm for 3, and characteristic sets of EPR signals due to the triplet states; |D/hc|=0.418, and 0.436 cm-1 and |E/hc|=0.021 and 0.022 cm-1 for 2 and 3, respectively. Diazo compound 4 after photolysis also showed absorptions at 506 and 471 nm and EPR signals characteristic of a quintet. Their complexes with Cu(hfac)2 showed a red shift of 3-14 nm in the visible spectra and gave EPR spectra characteristic of the high-spin complexes under similar conditions. Magnetic susceptibility measurements on a SQUID magnetometer were carried out using a sample similar to the one employed in the UV-Vis and EPR studies. The field dependence of magnetization in frozen solution suggested that the ground-state spin multiplicities of the photoproducts of 2, 3, and 4 were triplet, triplet, and quintet, respectively. Similarly, those of their complexes with Cu(hfac)2 were quartet, quintet, and septet, respectively.

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