3- and 4-(α-diazobenzyl)pyridine-: N -oxides as photoresponsive magnetic couplers for 2p-4f heterospin systems: Formation of carbene-TbIII and carbene-DyIII single-molecule magnets

Kensuke Murashima, Satoru Karasawa, Kenji Yoza, Yuji Inagaki, Noboru Koga

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

3- and 4-(α-diazophenyl)pyridine-N-oxides, 3- and 4-D1pyO, were prepared as new photoresponsive magnetic couplers in heterospin systems. Lanthanide dinuclear complexes, [LnIII(tta)3(4-D1pyO)]2; LnIII = Gd (1d), Tb (2d), and Dy (3d) and tta = 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate, bridged with 4-D1pyO in μ2 coordination mode were obtained. The obtained 1d, 2d, and 3d were isostructures. The isomeric complex, [TbIII(tta)3(3-D1pyO)]2 was also prepared. In the carbene-LnIII complexes [LnIII(tta)3(4- and 3-C1pyO)]2 generated by photolysis, C1pyO regioselectively interacted with the LnIII ions through pyridine-N-oxide, in which the magnetic coupling of 4-C1pyO was weakly ferromagnetic, while that of 3-C1pyO was insignificant. Before and after irradiation of 1d, no SMM behavior was observed. In contrast, the TbIII and DyIII complexes being anisotropic functioned as heterospin SMMs. Before irradiation, 2d showed no SMM behavior. After irradiation, two species showing slow magnetic relaxations were produced and one of them exhibited SMM behavior with the thermal activation barrier, Ueff/kB = 30 K, and τ0 = 5.8 × 10-8 s. In 3d, SMM behaviors were observed before and after irradiation, and the Ueff/kB value of 102 K (τ0 = 3.6 × 10-7 s) before irradiation was reduced to 39 K (τ0 = 1.5 × 10-8 s) after irradiation.

Original languageEnglish
Pages (from-to)7067-7077
Number of pages11
JournalDalton Transactions
Volume45
Issue number16
DOIs
Publication statusPublished - Apr 28 2016

Fingerprint

Magnets
Irradiation
Molecules
Magnetic relaxation
Magnetic couplings
Lanthanoid Series Elements
Photolysis
carbene
pyridine N-oxide
Chemical activation
Ions

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

3- and 4-(α-diazobenzyl)pyridine- : N -oxides as photoresponsive magnetic couplers for 2p-4f heterospin systems: Formation of carbene-TbIII and carbene-DyIII single-molecule magnets. / Murashima, Kensuke; Karasawa, Satoru; Yoza, Kenji; Inagaki, Yuji; Koga, Noboru.

In: Dalton Transactions, Vol. 45, No. 16, 28.04.2016, p. 7067-7077.

Research output: Contribution to journalArticle

@article{20c24d91090f43efa3fc8af458b73895,
title = "3- and 4-(α-diazobenzyl)pyridine-: N -oxides as photoresponsive magnetic couplers for 2p-4f heterospin systems: Formation of carbene-TbIII and carbene-DyIII single-molecule magnets",
abstract = "3- and 4-(α-diazophenyl)pyridine-N-oxides, 3- and 4-D1pyO, were prepared as new photoresponsive magnetic couplers in heterospin systems. Lanthanide dinuclear complexes, [LnIII(tta)3(4-D1pyO)]2; LnIII = Gd (1d), Tb (2d), and Dy (3d) and tta = 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate, bridged with 4-D1pyO in μ2 coordination mode were obtained. The obtained 1d, 2d, and 3d were isostructures. The isomeric complex, [TbIII(tta)3(3-D1pyO)]2 was also prepared. In the carbene-LnIII complexes [LnIII(tta)3(4- and 3-C1pyO)]2 generated by photolysis, C1pyO regioselectively interacted with the LnIII ions through pyridine-N-oxide, in which the magnetic coupling of 4-C1pyO was weakly ferromagnetic, while that of 3-C1pyO was insignificant. Before and after irradiation of 1d, no SMM behavior was observed. In contrast, the TbIII and DyIII complexes being anisotropic functioned as heterospin SMMs. Before irradiation, 2d showed no SMM behavior. After irradiation, two species showing slow magnetic relaxations were produced and one of them exhibited SMM behavior with the thermal activation barrier, Ueff/kB = 30 K, and τ0 = 5.8 × 10-8 s. In 3d, SMM behaviors were observed before and after irradiation, and the Ueff/kB value of 102 K (τ0 = 3.6 × 10-7 s) before irradiation was reduced to 39 K (τ0 = 1.5 × 10-8 s) after irradiation.",
author = "Kensuke Murashima and Satoru Karasawa and Kenji Yoza and Yuji Inagaki and Noboru Koga",
year = "2016",
month = "4",
day = "28",
doi = "10.1039/c6dt00420b",
language = "English",
volume = "45",
pages = "7067--7077",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "16",

}

TY - JOUR

T1 - 3- and 4-(α-diazobenzyl)pyridine-

T2 - N -oxides as photoresponsive magnetic couplers for 2p-4f heterospin systems: Formation of carbene-TbIII and carbene-DyIII single-molecule magnets

AU - Murashima, Kensuke

AU - Karasawa, Satoru

AU - Yoza, Kenji

AU - Inagaki, Yuji

AU - Koga, Noboru

PY - 2016/4/28

Y1 - 2016/4/28

N2 - 3- and 4-(α-diazophenyl)pyridine-N-oxides, 3- and 4-D1pyO, were prepared as new photoresponsive magnetic couplers in heterospin systems. Lanthanide dinuclear complexes, [LnIII(tta)3(4-D1pyO)]2; LnIII = Gd (1d), Tb (2d), and Dy (3d) and tta = 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate, bridged with 4-D1pyO in μ2 coordination mode were obtained. The obtained 1d, 2d, and 3d were isostructures. The isomeric complex, [TbIII(tta)3(3-D1pyO)]2 was also prepared. In the carbene-LnIII complexes [LnIII(tta)3(4- and 3-C1pyO)]2 generated by photolysis, C1pyO regioselectively interacted with the LnIII ions through pyridine-N-oxide, in which the magnetic coupling of 4-C1pyO was weakly ferromagnetic, while that of 3-C1pyO was insignificant. Before and after irradiation of 1d, no SMM behavior was observed. In contrast, the TbIII and DyIII complexes being anisotropic functioned as heterospin SMMs. Before irradiation, 2d showed no SMM behavior. After irradiation, two species showing slow magnetic relaxations were produced and one of them exhibited SMM behavior with the thermal activation barrier, Ueff/kB = 30 K, and τ0 = 5.8 × 10-8 s. In 3d, SMM behaviors were observed before and after irradiation, and the Ueff/kB value of 102 K (τ0 = 3.6 × 10-7 s) before irradiation was reduced to 39 K (τ0 = 1.5 × 10-8 s) after irradiation.

AB - 3- and 4-(α-diazophenyl)pyridine-N-oxides, 3- and 4-D1pyO, were prepared as new photoresponsive magnetic couplers in heterospin systems. Lanthanide dinuclear complexes, [LnIII(tta)3(4-D1pyO)]2; LnIII = Gd (1d), Tb (2d), and Dy (3d) and tta = 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate, bridged with 4-D1pyO in μ2 coordination mode were obtained. The obtained 1d, 2d, and 3d were isostructures. The isomeric complex, [TbIII(tta)3(3-D1pyO)]2 was also prepared. In the carbene-LnIII complexes [LnIII(tta)3(4- and 3-C1pyO)]2 generated by photolysis, C1pyO regioselectively interacted with the LnIII ions through pyridine-N-oxide, in which the magnetic coupling of 4-C1pyO was weakly ferromagnetic, while that of 3-C1pyO was insignificant. Before and after irradiation of 1d, no SMM behavior was observed. In contrast, the TbIII and DyIII complexes being anisotropic functioned as heterospin SMMs. Before irradiation, 2d showed no SMM behavior. After irradiation, two species showing slow magnetic relaxations were produced and one of them exhibited SMM behavior with the thermal activation barrier, Ueff/kB = 30 K, and τ0 = 5.8 × 10-8 s. In 3d, SMM behaviors were observed before and after irradiation, and the Ueff/kB value of 102 K (τ0 = 3.6 × 10-7 s) before irradiation was reduced to 39 K (τ0 = 1.5 × 10-8 s) after irradiation.

UR - http://www.scopus.com/inward/record.url?scp=84966359581&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84966359581&partnerID=8YFLogxK

U2 - 10.1039/c6dt00420b

DO - 10.1039/c6dt00420b

M3 - Article

AN - SCOPUS:84966359581

VL - 45

SP - 7067

EP - 7077

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 16

ER -